Process for the preparation of herbicidal derivatives

ABSTRACT

A process for the preparation of compounds of formula I  
                 
 
     wherein  
     R 0  is, each independently of any other, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 6 haloalkyl, cyano-C 1 -C 6 alkyl, C 2 -C 6 haloalkenyl, cyano-C 2 -C 6 alkenyl, C 2 -C 6 haloalkynyl, cyano-C 2 -C 6 alkynyl, hydroxy, hydroxy-C 1 -C 6 alkyl, C 1 -C 6 alkoxy, nitro, amino, C 1 -C 6 alkylamino, di(C 1 -C 6 alkyl)amino, C 1 -C 6 alkylcarbonylamino, C 1 -C 6 alkylsulfonylamino, C 1 -C 6 alkylaminosulfonyl, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkylcarbonyl-C 1 -C 6 alkyl, C 1 -C 6 alkoxycarbonyl-C 1 -C 6 alkyl, C 1 -C 6 alkylcarbonyl-C 2 -C 6 alkenyl, C 1 -C 6 alkoxycarbonyl-C 2 -C 6 alkenyl, C 1 -C 6 alkylcarbonyl-C 2 -C 6 alkynyl, C 1 -C 6 alkoxycarbonyl-C 2 -C 6 alkynyl, C 1 -C 6 alkoxycarbonyl, cyano, carboxyl, phenyl or an aromatic ring that contains 1 or 2 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, wherein the latter two aromatic rings may be substituted by C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, halogen, cyano or by nitro; or  
     R 0 , together with the adjacent substituents R 1 , R 2  and R 3 , forms a saturated or unsaturated C 3 -C 6 hydrocarbon bridge that may be interrupted by 1 or 2 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur and/or may be substituted by C 1 -C 4 alkyl;  
     R 1 , R 2  and R 3  are each independently of the others hydrogen, halogen, C 1 -C 6 alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 1 -C 6 alkoxycarbonyl-C 2 -C 6 alkenyl, C 1 -C 6 alkylcarbonyl-C 2 -C 6 alkenyl, cyano-C 2 -C 6 alkenyl, nitro-C 2 -C 6 -alkenyl, C 2 -C 6 haloalkynyl, C 1 -C 6 alkoxycarbonyl-C 2 -C 6 alkynyl, C 1 -C 6 alkylcarbonyl-C 2 -C 6 -alkynyl, cyano-C 2 -C 6 alkynyl, nitro-C 2 -C 6 alkynyl, C 3 -C 6 halocycloalkyl, hydroxy-C 1 -C 6 alkyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 1 -C 6 alkylthio-C 1 -C 6 alkyl, cyano, C 1 -C 4 alkylcarbonyl, C 1 -C 6 alkoxycarbonyl, hydroxy, C 1 -C 10 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, C 1 -C 6 haloalkoxy, C 3 -C 6 -haloalkenyloxy, C 1 -C 6 alkoxy-C 1 -C 6 alkoxy, mercapto, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 alkylsulfonyl, nitro, amino, C 1 -C 6 alkylamino, di(C 1 -C 6 alkyl)amino or phenoxy in which the phenyl ring may be substituted by C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 -alkoxy, C 1 -C 3 haloalkoxy, halogen, cyano or by nitro;  
     R 2  also may be phenyl, naphthyl or a 5- or 6-membered aromatic ring that may contain 1 or 2 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, wherein the phenyl ring, the naphthyl ring system and the 5- or 6-membered aromatic ring may be substituted by halogen, C 3 -C 8 cycloalkyl, hydroxy, mercapto, amino, cyano, nitro or by formyl; and/or  
     the phenyl ring, the naphthyl ring system and the 5- or 6-membered aromatic ring may be substituted by C 1 -C 6 alkyl, C 1 -C 6 alkoxy, hydroxy-C 1 -C 6 alkyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 1 -C 6 -alkoxy-C 1 -C 6 alkoxy, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 alkylsulfonyl, mono-C 1 -C 6 alkylamino, di(C 1 -C 6 alkyl)amino, C 1 -C 6 alkylcarbonylamino, C 1 -C 6 alkylcarbonyl-(C 1 -C 6 alkyl)amino, C 2 -C 6 alkenyl, C 3 -C 6 alkenyloxy, hydroxy-C 3 -C 6 alkenyl, C 1 -C 6 alkoxy-C 2 -C 6 -alkenyl, C 1 -C 6 alkoxy-C 3 -C 6 alkenyloxy, C 2 -C 6 alkenylcarbonyl, C 2 -C 6 alkenylthio, C 2 -C 6 alkenylsulfinyl, C 2 -C 6 alkenylsulfonyl, mono- or di-(C 2 -C 6 alkenyl)amino, C 1 -C 6 alkyl(C 3 -C 6 alkenyl)-amino, C 2 -C 6 alkenylcarbonylamino, C 2 -C 6 alkenylcarbonyl(C 1 -C 6 alkyl)amino, C 2 -C 6 alkynyl, C 3 -C 6 alkynyloxy, hydroxy-C 3 -C 6 alkynyl, C 1 -C 6 alkoxy-C 3 -C 6 alkynyl, C 1 -C 6 alkoxy-C 4 -C 6 alkynyloxy, C 2 -C 6 alkynylcarbonyl, C 2 -C 6 alkynylthio, C 2 -C 6 alkynylsulfinyl, C 2 -C 6 alkynylsulfonyl, mono- or di-(C 3 -C 6 alkynyl)amino, C 1 -C 6 alkyl(C 3 -C 6 alkynyl)amino, C 2 -C 6 alkynylcarbonylamino or by C 2 -C 6 alkynylcarbonyl(C 1 -C 6 alkyl)amino; and/or  
     the phenyl ring, the naphthyl ring system and the 5- or 6-membered aromatic ring may be substituted by halo-substituted C 1 -C 6 alkyl, C 1 -C 6 alkoxy, hydroxy-C 1 -C 6 alkyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 1 -C 6 alkoxy-C 1 -C 6 alkoxy, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 alkylsulfonyl, mono-C 1 -C 6 alkylamino, di(C 1 -C 6 alkyl)amino, C 1 -C 6 alkylcarbonylamino, C 1 -C 6 alkylcarbonyl(C 1 -C 6 alkyl)amino, C 2 -C 6 alkenyl, C 3 -C 6 alkenyloxy, hydroxy-C 3 -C 6 alkenyl, C 1 -C 6 alkoxy-C 2 -C 6 alkenyl, C 1 -C 6 alkoxy-C 3 -C 6 alkenyloxy, C 2 -C 6 alkenylcarbonyl, C 2 -C 6 alkenylthio, C 2 -C 6 alkenylsulfinyl, C 2 -C 6 alkenylsulfonyl, mono- or di-(C 2 -C 6 alkenyl)amino, C 1 -C 6 alkyl-(C 3 -C 6 alkenyl)amino, C 2 -C 6 alkenylcarbonylamino, C 2 -C 6 alkenylcarbonyl(C 1 -C 6 alkyl)amino, C 2 -C 6 alkynyl, C 3 -C 6 alkynyloxy, hydroxy-C 3 -C 6 alkynyl, C 1 -C 6 alkoxy-C 3 -C 6 alkynyl, C 1 -C 6 alkoxy-C 4 -C 6 alkynyloxy, C 2 -C 6 alkynylcarbonyl, C 2 -C 6 alkynylthio, C 2 -C 6 alkynylsulfinyl, C 2 -C 6 alkynylsulfonyl, mono- or di-(C 3 -C 6 alkynyl)amino, C 1 -C 6 alkyl(C 3 -C 6 alkynyl)amino, C 2 -C 6 alkynylcarbonylamino or C 2 -C 6 alkynylcarbonyl(C 1 -C 6 alkyl)amino; and/or  
     the phenyl ring, the naphthyl ring system and the 5- or 6-membered aromatic ring may be substituted by a radical of the formula COOR 50 , CONR 51 , SO 2 NR 53 R 54  or SO 2 OR 55  wherein R 50 , R 51 , R 52 , R 53 , R 54  and R 55  are each independently of the others C 1 -C 6 alkyl, C 2 -C 6 alkenyl or C 3 -C 6 alkynyl or halo-, hydroxy-, alkoxy-, mercapto-, amino-, cyano-, nitro-, alkylthio-, alkylsulfinyl- or alkylsulfonyl-substituted C 1 -C 6 alkyl, C 2 -C 6 alkenyl or C 3 -C 6 alkynyl;  
     n is 0, 1 or 2; and R 4 , R 5  and G are each as defined in claim 1, which process comprises reacting a compound of formula II  
                 
 
     wherein R 0 , R 1 , R 2 , R 3  and n are as defined hereinbefore; R 6  is R 8 R 9 N—; R 7  is R 10 R 11 N— or R 12 O—; and R 8 , R 9 , R 10 , R 11  and R 12  are each independently of the others hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 alkenyl or benzyl, wherein the phenyl ring of the benzyl group may be substituted by C 1 -C 4 alkyl, halogen, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or by nitro, in an inert organic solvent, optionally in the presence of a base, with a compound of formula IV, IVa or IVb  
                 
 
     wherein R 4  and R 5  are as defined hereinbefore and H.Hal is a hydrogen halide, and optionally converting the resulting compound of formula I wherein G is a metal ion equivalent or an ammonium cation, by salt conversion into the corresponding salt of formula I wherein  
     G is a sulfonium or phosphonium cation, or by treatment with a Brönsted acid into the corresponding compound of formula I wherein G is hydrogen, and  
     ‘in situ’ conversion of compounds of formula I with an electrophile of formula XII or XIId  
     G 0 -L  (XII)  
     or  
     R 32 —N═C═X 3   (XIId),  
     wherein G 0 , R 32  and X 3  are as defined hereinbefore except that R 32  is not hydrogen, and L is a leaving group, optionally in the presence of an acid-binding agent or a catalyst, to the compounds of formula Ia  
                 
 
     wherein R 0 , R 1 , R 2 , R 3 , R 4 , R 5  and n are as defined for formula I;  
     G 0  is a group —C(O)—R 30 , —C(X 1 )—X 2 —R 31 , —C(X 3 )—N(R 32 )—R 33 , —SO 2 —R 34  or —P(X 4 )(R 35 )—R 36 ; and X 1 , X 2 , X 3 , X 4 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35  and R 36  are as defined hereinbefore.

[0001] The present invention relates to a new process for thepreparation of herbicidally active substituted3-hydroxy-4-aryl-5-oxopyrazoline derivatives.

[0002] 3-Hydroxy-4-aryl-5-oxopyrazolines having herbicidal action andthe preparation thereof are described, for example, in WO 92/16510,EP-A-0 508 126, WO 95/01971, WO 96/21652, WO 96/25395, WO 97/02243 andin WO 99/47525.

[0003] Surprisingly, it has now been found that substituted3-hydroxy-4-aryl-5-oxopyrazoline derivatives can readily be prepared ina high yield and with a high degree of purity by the condensation ofarylmalonic acid diamides or arylmalonic acid monoamides with hydrazinederivatives.

[0004] The present invention accordingly relates to a process for thepreparation of compounds of formula I

[0005] wherein

[0006] R₀ is, each independently of any other, halogen, C₁-C₆alkyl,C₂-C₆alkenyl, C₂-C₆alkynyl, C₁-C₆haloalkyl, cyano-C₁-C₆alkyl,C₂-C₆haloalkenyl, cyano-C₂-C₆alkenyl, C₂-C₆haloalkynyl,cyano-C₂-C₆alkynyl, hydroxy, hydroxy-C₁-C₆alkyl, C₁-C₆alkoxy, nitro,amino, C₁-C₆alkylamino, di(C₁-C₆alkyl)amino, C₁-C₆alkylcarbonylamino,C₁-C₆alkylsulfonylamino, C₁-C₆alkylaminosulfonyl, C₁-C₆alkylcarbonyl,C₁-C₆alkylcarbonyl-C₁-C₆alkyl, C₁-C₆alkoxycarbonyl-C₁-C₆alkyl,C₁-C₆alkylcarbonyl-C₂-C₆alkenyl, C₁-C₆alkoxycarbonyl-C₂-C₆alkenyl,C₁-C₆alkylcarbonyl-C₂-C₆alkynyl, C₁-C₆alkoxycarbonyl-C₂-C₆alkynyl,C₁-C₆alkoxycarbonyl, cyano, carboxyl, phenyl or an aromatic ring thatcontains 1 or 2 hetero atoms selected from the group consisting ofnitrogen, oxygen and sulfur, wherein the latter two aromatic rings maybe substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,C₁-C₃haloalkoxy, halogen, cyano or by nitro; or

[0007] R₀, together with the adjacent substituents R₁, R₂ and R₃, formsa saturated or unsaturated C₃-C₆hydrocarbon bridge that may beinterrupted by 1 or 2 hetero atoms selected from the group consisting ofnitrogen, oxygen and sulfur and/or may be substituted by C₁-C₄alkyl; R₁,R₂ and R₃ are each independently of the others hydrogen, halogen,C₁-C₆alkyl, C₂-C₆-alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl,C₁-C₆haloalkyl, C₂-C₆haloalkenyl, C₁-C₆alkoxycarbonyl-C₂-C₆alkenyl,C₁-C₆alkylcarbonyl-C₂-C₆alkenyl, cyano-C₂-C₆alkenyl,nitro-C₂-C₆-alkenyl, C₂-C₆haloalkynyl, C₁-C₆alkoxycarbonyl-C₂-C₆alkynyl,C₁-C₆alkylcarbonyl-C₂-C₆-alkynyl, cyano-C₂-C₆alkynyl,nitro-C₂-C₆alkynyl, C₃-C₆halocycloalkyl, hydroxy-C₁-C₆alkyl,C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆alkylthio-C₁-C₆alkyl, cyano,C₁-C₄alkylcarbonyl, C₁-C₆alkoxycarbonyl, hydroxy, C₁-C₁₀alkoxy,C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C₁-C₆haloalkoxy, C₃-C₆-haloalkenyloxy,C₁-C₆alkoxy-C₁-C₆alkoxy, mercapto, C₁-C₆alkylthio, C₁-C₆haloalkylthio,C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, nitro, amino, C₁-C₆alkylamino,di(C₁-C₆alkyl)amino or phenoxy in which the phenyl ring may besubstituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃-alkoxy,C₁-C₃haloalkoxy, halogen, cyano or by nitro;

[0008] R₂ also may be phenyl, naphthyl or a 5- or 6-membered aromaticring that may contain 1 or 2 hetero atoms selected from the groupconsisting of nitrogen, oxygen and sulfur, wherein the phenyl ring, thenaphthyl ring system and the 5- or 6-membered aromatic ring may besubstituted by halogen, C₃-C₈cycloalkyl, hydroxy, mercapto, amino,cyano, nitro or by formyl; and/or

[0009] the phenyl ring, the naphthyl ring system and the 5- or6-membered aromatic ring may be substituted by C₁-C₆alkyl, C₁-C₆alkoxy,hydroxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆-alkoxy-C₁-C₆alkoxy,C₁-C₆alkylcarbonyl, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl,C₁-C₆alkylsulfonyl, mono-C₁-C₆alkylamino, di(C₁-C₆alkyl)amino,C₁-C₆alkylcarbonylamino, C₁-C₆alkylcarbonyl-(C₁-C₆alkyl)amino,C₂-C₆alkenyl, C₃-C₆alkenyloxy, hydroxy-C₃-C₆alkenyl,C₁-C₆alkoxy-C₂-C₆-alkenyl, C₁-C₆alkoxy-C₃-C₆alkenyloxy,C₂-C₆alkenylcarbonyl, C₂-C₆alkenylthio, C₂-C₆alkenylsulfinyl,C₂-C₆alkenylsulfonyl, mono- or di-(C₂-C₆alkenyl)amino,C₁-C₆alkyl(C₃-C₆alkenyl)-amino, C₂-C₆alkenylcarbonylamino,C₂-C₆alkenylcarbonyl(C₁-C₆alkyl)amino, C₂-C₆alkynyl, C₃-C₆alkynyloxy,hydroxy-C₃-C₆alkynyl, C₁-C₆alkoxy-C₃-C₆alkynyl,C₁-C₆alkoxy-C₄-C₆alkynyloxy, C₂-C₆alkynylcarbonyl, C₂-C₆alkynylthio,C₂-C₆alkynylsulfinyl, C₂-C₆alkynylsulfonyl, mono- ordi-(C₃-C₆alkynyl)amino, C₁-C₆alkyl(C₃-C₆alkynyl)amino,C₂-C₆alkynylcarbonylamino or by C₂-C₆alkynylcarbonyl(C₁-C₆alkyl)amino;and/or

[0010] the phenyl ring, the naphthyl ring system and the 5- or6-membered aromatic ring may be substituted by halo-substitutedC₁-C₆alkyl, C₁-C₆alkoxy, hydroxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl,C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆alkylcarbonyl, C₁-C₆alkylthio,C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, mono-C₁-C₆alkylamino,di(C₁-C₆alkyl)amino, C₁-C₆alkylcarbonylamino,C₁-C₆alkylcarbonyl(C₁-C₆alkyl)amino, C₂-C₆alkenyl, C₃-C₆alkenyloxy,hydroxy-C₃-C₆alkenyl, C₁-C₆alkoxy-C₂-C₆alkenyl,C₁-C₆alkoxy-C₃-C₆alkenyloxy, C₂-C₆alkenylcarbonyl, C₂-C₆alkenylthio,C₂-C₆alkenylsulfinyl, C₂-C₆alkenylsulfonyl, mono- ordi-(C₂-C₆alkenyl)amino, C₁-C₆alkyl-(C₃-C₆alkenyl)amino,C₂-C₆alkenylcarbonylamino, C₂-C₆alkenylcarbonyl(C₁-C₆alkyl)amino,C₂-C₆alkynyl, C₃-C₆alkynyloxy, hydroxy-C₃-C₆alkynyl,C₁-C₆alkoxy-C₃-C₆alkynyl, C₁-C₆alkoxy-C₄-C₆alkynyloxy,C₂-C₆alkynylcarbonyl, C₂-C₆alkynylthio, C₂-C₆alkynylsulfinyl,C₂-C₆alkynylsulfonyl, mono- or di-(C₃-C₆alkynyl)amino,C₁-C₆alkyl(C₃-C₆alkynyl)amino, C₂-C₆alkynylcarbonylamino orC₂-C₆alkynylcarbonyl(C₁-C₆alkyl)amino; and/or

[0011] the phenyl ring, the naphthyl ring system and the 5- or6-membered aromatic ring may be substituted by a radical of the formulaCOOR₅₀, CONR₅₁, SO₂NR₅₃R₅₄ or SO₂OR₅₅ wherein R₅₀, R₅₁, R₅₂, R₅₃, R₅₄and R₅₅ are each independently of the others C₁-C₆alkyl, C₂-C₆alkenyl orC₃-C₆alkynyl or halo-, hydroxy-, alkoxy-, mercapto-, amino-, cyano-,nitro-, alkylthio-, alkylsulfinyl- or alkylsulfonyl-substitutedC₁-C₆alkyl, C₂-C₆alkenyl or C₃-C₆alkynyl;

[0012] n is 0, 1 or 2;

[0013] R₄ and R₅ are each independently of the other hydrogen,C₁-C₁₂alkyl, C₁-C₁₂haloalkyl, C₂-C₈-alkenyl, C₂-C₈alkynyl,C₁-C₁₀alkoxy-C₁-C₈alkyl, poly-C₁-C₁₀alkoxy-C₁-C₈alkyl,C₁-C₁₀alkylthio-C₁-C₈alkyl, C₃-C₈cycloalkyl, C₃-C₈halocycloalkyl, 4- to8-membered heterocyclyl, phenyl, α- or β-naphthyl, phenyl-C₁-C₆alkyl, α-or β-naphthyl-C₁-C₆alkyl, 5- or 6-membered heteroaryl or 5- or6-membered heteroaryl-C₁-C₆alkyl, wherein those aromatic andheteroaromatic rings may be substituted by halogen, C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, nitro or by cyano; or

[0014] R₄ and R₅, together with the nitrogen atoms to which they arebonded, form a saturated or unsaturated 5- to 8-membered heterocyclicring that 1) may be interrupted by oxygen, sulfur or by —NR₁₄— and/ormay be substituted by halogen, C₁-C₁₀alkyl, C₁-C₁₀haloalkyl, hydroxy,C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆haloalkoxy, mercapto,C₁-C₆alkylthio, C₃-C₇-cycloalkyl, heteroaryl, heteroaryl-C₁-C₆alkyl,phenyl, phenyl-C₁-C₆alkyl or by benzyloxy, wherein the phenyl rings ofthe last three substituents may in turn be substituted by halogen,C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy or by nitro,and/or 2) may contain a fused or spiro-bound alkylene or alkenylenechain having from 2 to 6 carbon atoms that is optionally interrupted byoxygen or by sulfur, or at least one ring atom of the saturated orunsaturated heterocyclic ring bridges that alkylene or alkenylene chain;R₁₄ is hydrogen, C₁-C₄alkyl, C₁-C₆alkylcarbonyl, C₁-C₆alkylsulfonyl,C₃-C₆alkenyl or C₃-C₆alkynyl; and

[0015] G is hydrogen, a metal ion equivalent or an ammonium, sulfoniumor phosphonium cation, which comprises reacting a compound of formula II

[0016] wherein R₀, R₁, R₂, R₃ and n are as defined hereinbefore; R₆ isR₈R₉N—; R₇ is R₁₀R₁₁N— or R₁₂O—; and R₈, R₉, R₁₀, R₁₁ and R₁₂ are eachindependently of the others hydrogen, C₁-C₆-alkyl, C₁-C₆haloalkyl,C₃-C₆alkenyl or benzyl, wherein the phenyl ring of the benzyl group maybe substituted by C₁-C₄alkyl, halogen, C₁-C₄haloalkyl, C₁-C₄alkoxy or bynitro, in an inert organic solvent, optionally in the presence of abase, with a compound of formula IV, IVa or IVb

[0017] wherein R₄ and R₅ are as defined hereinbefore and H.Hal is ahydrogen halide, and optionally converting the resulting compound offormula I wherein G is a metal ion equivalent or an ammonium cation, bysalt conversion into the corresponding salt of formula I wherein G is asulfonium or phosphonium cation, or by treatment with a Brönsted acidinto the corresponding compound of formula I wherein G is hydrogen.

[0018] The present invention relates also to the direct (‘in situ’)conversion, in a one-pot reaction, of compounds of formula I tocompounds of formula Ia

[0019] wherein R₀, R₁, R₂, R₃, R₄, R₅ and n are as defined for formulaI;

[0020] G₀ is a group —C(O)—R₃₀, —C(X₁)—X₂—R₃₁, —C(X₃)—N(R₃₂)—R₃₃,—SO₂—R₃₄ or —P(X₄)(R₃₅)—R₃₆;

[0021] X₁, X₂, X₃ and X₄ are each independently of the others oxygen orsulfur;

[0022] R₃₀ is unsubstituted or halo-substituted C₁-C₂₀alkyl,C₂-C₂₀alkenyl, C₁-C₈alkoxy-C₁-C₈alkyl, C₁-C₈alkylthio-C₁-C₈alkyl,poly-C₁-C₈alkoxy-C₁-C₈alkyl or unsubstituted or halo-, C₁-C₆alkyl- orC₁-C₆alkoxy-substituted C₃-C₈cycloalkyl, in which optionally at leastone ring member has been replaced by oxygen and/or by sulfur,C₃-C₆cycloalkyl-C₁-C₆alkyl, heterocyclyl-C₁-C₆-alkyl,heteroaryl-C₁-C₆alkyl, unsubstituted or halo-, cyano-, nitro-,C₁-C₆alkyl-, C₁-C₆alkoxy-, C₁-C₆haloalkyl-, C₁-C₆haloalkoxy-,C₁-C₆alkylthio- or C₁-C₆alkylsulfonyl-substituted phenyl, unsubstitutedor halo-, nitro-, cyano-, C₁-C₆alkyl-, C₁-C₆alkoxy-, C₁-C₆haloalkyl- orC₁-C₆haloalkoxy-substituted phenyl-C₁-C₆alkyl, unsubstituted or halo- orC₁-C₆alkyl-substituted heteroaryl, unsubstituted or halo- orC₁-C₆alkyl-substituted phenoxy-C₁-C₆alkyl, or unsubstituted or halo-,amino- or C₁-C₆alkyl-substituted heteroaryloxy-C₁-C₆alkyl;

[0023] R₃₁ is unsubstituted or halo-substituted C₁-C₂₀alkyl,C₂-C₂₀alkenyl, C₁-C₈alkoxy-C₂-C₈alkyl, poly-C₁-C₈alkoxy-C₂-C₈alkyl,unsubstituted or halo-, C₁-C₆alkyl- or C₁-C₆alkoxy-substitutedC₃-C₈cycloalkyl, C₃-C₆cycloalkyl-C₁-C₆alkyl, heterocyclyl-C₁-C₆alkyl,heteroaryl-C₁-C₆alkyl, unsubstituted or halo-, cyano-, nitro-,C₁-C₆alkyl-, C₁-C₆alkoxy-, C₁-C₆haloalkyl- orC₁-C₆-haloalkoxy-substituted phenyl or benzyl;

[0024] R₃₂ and R₃₃ are each independently of the other hydrogen,unsubstituted or halo-substituted C₁-C₈alkyl, C₃-C₈cycloalkyl,C₁-C₈alkoxy, C₃-C₈alkenyl, C₁-C₈alkoxy-C₁-C₈alkyl, unsubstituted orhalo-, C₁-C₈haloalkyl-, C₁-C₈alkyl- or C₁-C₈alkoxy-substituted phenyl orbenzyl; or

[0025] R₃₂ and R₃₃ together form a C₃-C₆alkylene chain in which a carbonatom has optionally been replaced by oxygen or by sulfur;

[0026] R₃₄ is unsubstituted or halo-substituted C₁-C₈alkyl,C₃-C₈alkenyl, C₃-C₈haloalkenyl, C₃-C₈-alkynyl, C₃-C₈haloalkynyl, orunsubstituted or halo-, C₁-C₆alkyl-, C₁-C₆alkoxy-, C₁-C₄haloalkyl-,C₁-C₄haloalkoxy-, cyano- or nitro-substituted phenyl or benzyl;

[0027] R₃₅ and R₃₆ are each independently of the other unsubstituted orhalo-substituted C₁-C₈alkyl, C₁-C₈alkoxy, C₁-C₈alkylamino,di(C₁-C₈alkyl)amino, C₁-C₈alkylthio, C₂-C₈alkenylthio,C₃-C₇-cycloalkylthio, or unsubstituted or halo-, nitro-, cyano-,C₁-C₄alkoxy-, C₁-C₄haloalkoxy-, C₁-C₄alkylthio-, C₁-C₄haloalkylthio-,C₁-C₄alkyl- or C₁-C₄haloalkyl-substituted phenyl, phenoxy or phenylthio,

[0028] which conversion comprises reacting compounds of formula I,optionally in the presence of an acid-binding agent or a catalyst, withan electrophile of formula XII or XIId

G₀-L  (XII)

or

R₃₂—N═C═X₃  (XIId),

[0029] wherein G₀, R₃₂ and X₃ are as defined hereinbefore except thatR₃₂ is not hydrogen, and L is a leaving group, for example R₃₀C(O)O—,R₃₁X₂— or halogen, preferably chlorine, bromine or iodine.

[0030] Depending on the substituents R₀ to R₅, G and G₀, the compoundsof formulae I and Ia may be in the form of geometric and/or opticalisomers or isomeric mixtures (atropisomers) and, when G is hydrogen, ametal ion equivalent, or an ammonium, sulfonium or phosphonium cation,they may be in the form of tautomers or tautomeric mixtures.

[0031] If the starting materials employed are not enantiomerically pure,the compounds of formulae I and Ia obtained in the above-describedprocesses are generally in the form of racemates or diastereoisomericmixtures which, if desired, can be separated on the basis of theirphysico-chemical properties according to known methods, such as, forexample, fractional crystallisation following salt formation withoptically pure bases, acids or metal complexes, or by chromatographicprocedures, such as, for example, high-pressure liquid chromatography(HPLC) on acetyl cellulose.

[0032] In the present invention, the compounds of formulae I and Ia areto be understood as both the enriched and optically pure forms of therespective stereoisomers as well as the racemates and diastereoisomers.Unless there is specific reference to the individual optical antipodes,the given formulae are to be understood as the racemic mixtures thathave been obtained by the preparation process according to theinvention. When an aliphatic C═C double bond is present, geometricisomerism may also occur.

[0033] The present invention relates also to the salts that thecompounds of formulae I and Ia are able to form with acids. Suitableacids for the formation of the acid addition salt include both organicand inorganic acids. Examples of such acids are hydrochloric acid,hydrobromic acid, nitric acid, phosphoric acids, sulfuric acid, aceticacid, propionic acid, butyric acid, valeric acid, oxalic acid, malonicacid, fumaric acid, organic sulfonic acids, lactic acid, tartaric acid,citric acid and salicylic acid.

[0034] In view of their acidity, the compounds of formula I wherein G ishydrogen can readily be converted in the presence of bases (protonacceptors) into the corresponding salts (wherein G is, for example, ametal ion equivalent or an ammonium cation), as described, for example,in EP-A-0 508 126. Any customary proton acceptor may be used as base.The salts are, for example, alkali metal salts, for example sodium andpotassium salts; alkaline earth metal salts, for example calcium andmagnesium salts; ammonium salts, that is to say, unsubstituted ammoniumsalts and mono- or poly-substituted ammonium salts, for exampletriethylammonium and methylammonium salts, or salts with other organicbases or other cations, for example sulfonium or phosphonium cations.Sulfonium cations include, for example, tri(C₁-C₄alkyl)sulfoniumcations, which can be obtained from the corresponding alkali metalsalts, for example, by salt conversion, for example using a cationexchanger.

[0035] Among the alkali metal and alkaline earth metal hydroxides assalt formers, special mention may be made, for example, of thehydroxides of lithium, sodium, potassium, magnesium and calcium, butespecially the hydroxides of sodium and potassium. Suitable salt formersare described, for example, in WO 97/41112.

[0036] Examples of suitable amines for ammonium salt formation includeboth ammonia and primary, secondary and tertiary C₁-C₁₈alkylamines,C₁-C₄-hydroxyalkylamines and C₂-C₄-alkoxyalkylamines, for examplemethylamine, ethylamine, n-propylamine, isopropylamine, the fourbutylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine,octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine,heptadecylamine, octadecylamine, methyl-ethylamine,methyl-isopropylamine, methyl-hexylamine, methyl-nonylamine,methyl-pentadecylamine, methyl-octadecylamine, ethyl-butylamine,ethyl-heptylamine, ethyl-octylamine, hexyl-heptylamine,hexyl-octylamine, dimethylamine, diethylamine, di-n-propylamine,diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine,dihexylamine, diheptylamine, dioctylamine, ethanolamine,n-propanolamine, isopropanolamine, N,N-diethanolamine,N-ethylpropanolamine, N-butylethanolamine, allylamine,n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine,dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine,triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine,triisobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamineand ethoxyethylamine; heterocyclic amines, for example pyridine,quinoline, isoquinoline, morpholine, N-methylmorpholine, thiomorpholine,piperidine, pyrrolidine, indoline, quinuclidine and azepine; primaryarylamines, for example anilines, methoxyanilines, ethoxyanilines, o-,m- and p-toluidines, phenylenediamines, benzidines, naphthylamines ando-, m- and p-chloroanilines; but especially triethylamine,isopropylamine and diisopropylamine.

[0037] In the above definitions, halogen is to be undertstood asfluorine, chlorine, bromine or iodine, preferably fluorine, chorine orbromine.

[0038] The alkyl groups occurring in the substituent definitions are,for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,isobutyl or tert-butyl, and the pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl and dodecyl isomers.

[0039] Haloalkyl groups preferably have a chain length of from 1 to 6carbon atoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl,difluorochloromethyl, trifluoromethyl, chloromethyl, dichloromethyl,dichlorofluoromethyl, trichloromethyl, 2,2,2-trifluoroethyl,2-fluoroethyl, 2-chloroethyl, 2,2-difluoroethyl, 2,2-dichloroethyl,2,2,2-trichloroethyl or pentafluoroethyl, preferably trichloromethyl,difluoromethyl, difluorochloromethyl, trifluoromethyl ordichlorofluoromethyl.

[0040] Alkoxy groups preferably have a chain length of from 1 to 6carbon atoms. Alkoxy is, for example, methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy or a pentyloxyor hexyloxy isomer, preferably methoxy, ethoxy or n-propoxy.

[0041] Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy,trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy,2-fluoroethoxy, 2-chloroethoxy or 2,2,2-trichloroethoxy.

[0042] There may be mentioned as examples of alkenyl radicals vinyl,allyl, methallyl, 1-methylvinyl, but-2-en-1-yl, pentenyl and 2-hexenyl;preferably alkenyl radicals having a chain length of from 3 to 6 carbonatoms.

[0043] There may be mentioned as examples of alkynyl radicals ethynyl,propargyl, 1-methylpropargyl, 3-butynyl, but-2-yn-1-yl,2-methylbut-3-yn-2-yl, but-3-yn-2-yl, 1-pentynyl, pent-4-yn-1-yl and2-hexynyl; preferably alkynyl radicals having a chain length of from 3to 6 carbon atoms.

[0044] Suitable haloalkenyl radicals include alkenyl groups substitutedone or more times by halogen, halogen being in particular bromine oriodine and especially fluorine or chlorine, for example 2- and3-fluoropropenyl, 2- and 3-chloropropenyl, 2- and 3-bromopropenyl,2,2-difluoro-1-methylvinyl, 2,3,3-trifluoropropenyl,3,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl,4,4,4-trifluorobut-2-en-1-yl and 4,4,4-trichlorobut-2-en-1-yl. Preferredalkenyl radicals substituted once, twice or three times by halogen arethose having a chain length of from 3 to 6 carbon atoms. The alkenylgroups may be substituted by halogen at saturated or unsaturated carbonatoms.

[0045] Suitable haloalkynyl groups include, for example, alkynyl groupssubstituted one or more times by halogen, halogen being bromine oriodine and especially fluorine or chlorine, for example3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl and4,4,4-trifluorobut-2-yn-1-yl.

[0046] Alkenyloxy is, for example, allyloxy, methallyloxy orbut-2-en-1-yloxy.

[0047] Alkynyloxy is, for example, propargyloxy or 1-methylpropargyloxy.

[0048] Suitable haloalkenyloxy groups include alkenyloxy groupssubstituted one or more times by halogen, halogen being in particularbromine or iodine and especially fluorine or chlorine, for example 2-and 3-fluoropropenyloxy, 2- and 3-chloropropenyloxy, 2- and3-bromopropenyloxy, 2,3,3-trifluoropropenyloxy,2,3,3-trichloropropenyloxy, 4,4,4-trifluorobut-2-en-1-yloxy and4,4,4-trichlorobut-2-en-1-yloxy.

[0049] Alkoxyalkyl groups have preferably from 1 to 6 carbon atoms.Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl,ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl orisopropoxyethyl.

[0050] Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy,trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy,2-fluoroethoxy, 2-chloroethoxy or 2,2,2-trichloroethoxy.

[0051] Polyalkoxy-alkyl is, for example, methoxymethoxy-methyl,ethoxymethoxy-methyl, ethoxyethoxy-methyl, n-propoxyethoxy-methyl,isopropoxyethoxy-methyl, methoxymethoxy-ethyl, ethoxymethoxy-ethyl,ethoxyethoxy-ethyl, n-propoxyethoxy-methyl, n-propoxyethoxy-ethyl,isopropoxyethoxy-methyl, isopropoxyethoxy-ethyl or (ethoxy)₃-ethyl.

[0052] Suitable cycloalkyl substituents contain from 3 to 8 carbon atomsand are, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl or cyclooctyl. They may be substituted one or more times byhalogen, preferably fluorine, chlorine and/or bromine.

[0053] Alkylcarbonyl is especially acetyl or propionyl.

[0054] Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl,n-propoxycarbonyl, isopropoxycarbonyl or a butoxycarbonyl,pentyloxycarbonyl or hexyloxycarbonyl isomer, preferably methoxycarbonylor ethoxycarbonyl.

[0055] Phenyl, phenoxy and naphthyl may be in substituted form, in whichcase the substituents may, as desired, be in the ortho-, meta- and/orpara-position and, in the case of the naphthyl ring system, in additionin the 5-, 6-, 7- and/or 8-position. Preferred positions for thesubstituents are the ortho- and para-position to the ring attachmentpoint. Where the phenyl, phenoxy and naphthyl substituents are notexplicitly mentioned they are, for example, C₁-C₄-alkyl, halogen,C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, nitro, cyano, amino,C₁-C₄alkylamino or di(C₁-C₄alkyl)amino.

[0056] Alkylthio groups preferably have a chain length of from 1 to 6carbon atoms. Alkylthio is, for example, methylthio, ethylthio,propylthio, butylthio, pentylthio or hexylthio, or a branched isomerthereof, but is preferably methylthio or ethylthio.

[0057] Haloalkylthio is, for example, 2,2,2-trifluoroethylthio or2,2,2-trichloroethylthio.

[0058] Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl,n-propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl,sec-butylsulfinyl or tert-butylsulfinyl; preferably methylsulfinyl orethylsulfinyl.

[0059] Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl,n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl,sec-butylsulfonyl or tert-butylsulfonyl; preferably methylsulfonyl orethylsulfonyl.

[0060] Alkylamino is, for example, methylamino, ethylamino,n-propylamino, isopropylamino or a butyl-, pentyl- or hexyl-amineisomer.

[0061] Dialkylamino is, for example, dimethylamino, methylethylamino,diethylamino, n-propylmethylamino, dibutylamino or diisopropylamino.

[0062] Alkylthioalkyl is, for example, methylthiomethyl,methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propylthiomethyl,n-propylthioethyl, isopropylthiomethyl or isopropylthioethyl.

[0063] Heterocyclyl radicals are preferably 4- to 8-membered rings thatcontain 1 or 2 hetero atoms, for example N, S and/or O. They are usuallysaturated.

[0064] Heteroaryl radicals are usually 5- or 6-membered aromaticheterocycles that contain preferably from 1 to 3 hetero atoms, such asN, S and/or O. The following are examples of suitable heterocyclyl andheteroaryl radicals: pyridyl, pyrrolidyl, piperidyl, pyranyl, dioxanyl,azetidyl, oxetanyl, pyrimidyl, triazinyl, thiazolyl, triazolyl,thiadiazolyl, imidazolyl, oxazolyl, isoxazolyl, pyrazinyl, furyl,thienyl, morpholyl, piperazinyl, pyrazolyl, benzoxazolyl,benzothiazolyl, quinoxalyl, indolyl and quinolyl. Those heterocycles andheteroaromatic radicals may in addition be substituted, thesubstituents, where they are not explicitly mentioned, being, forexample, halogen, C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆haloalkyl,C₁-C₆haloalkoxy, C₁-C₆alkylthio, amino, C₁-C₆alkylamino,di(C₁-C₆alkyl)amino, phenyl, nitro or cyano.

[0065] The substituent definition according to which “R₄ and R₅,together with the nitrogen atoms to which they are bonded, form asaturated or unsaturated, 5- to 8-membered heterocyclic ring that 1) maybe interrupted by oxygen, sulfur or by —NR₁₄— and/or may be substitutedby halogen, C₁-C₁₀alkyl, C₁-C₁₀haloalkyl, hydroxy, C₁-C₆alkoxy,C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆-haloalkoxy, mercapto, C₁-C₆alkylthio,C₃-C₇cycloalkyl, heteroaryl, heteroaryl-C₁-C₆alkyl, phenyl,phenyl-C₁-C₆alkyl or by benzyloxy, wherein the phenyl rings of the lastthree substituents may in turn be substituted by halogen, C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy or by nitro, and/or 2) maycontain a fused or spiro-bound alkylene or alkenylene chain having from2 to 6 carbon atoms that is optionally interrupted by oxygen or bysulfur, or at least one ring atom of the saturated or unsaturatedheterocyclic ring bridges that alkylene or alkenylene chain”, signifies,for example, the following heterocyclic ring systems:

[0066] In the above polycyclic rings systems, the abbreviatedrepresentation

[0067] denotes the group

[0068] The 5- to 8-membered heterocyclic rings that the substituents R₄and R₅ together may form and the fused or spiro-bound alkylene oralkenylene chains having from 2 to 6 carbon atoms may accordingly beinterrupted once or twice by hetero atoms, such as, for example, oxygen.

[0069] Meanings corresponding to those given hereinbefore can also beascribed to the substituents in composite definitions, such as, forexample, alkoxy-alkoxy, alkyl-sulfonylamino, alkyl-aminosulfonyl,alkoxy-carbonyl, alkyl-carbonylamino, phenyl-alkyl, naphthyl-alkyl andheteroaryl-alkyl.

[0070] In the definitions of alkylcarbonyl, alkylcarbonylamino andalkoxycarbonyl, the carbon atom of the carbonyl is not included in thelower and upper limits given for the number of carbon atoms in eachparticular case.

[0071] The composite definitions that may arise in respect of theradicals R₃₀, R₃₁ and R₃₄ in substituent G₀ in formula Ia, such as, forexample, cycloalkyl-thio, cycloalkyl-alkyl, heterocyclyl-alkyl,heteroaryl-alkyl, phenyl-alkyl, phenoxy-alkyl and heteroaryloxy-alkylradicals, are derived from the corresponding radicals of the radicalsmentioned above.

[0072] Heterocyclyl radicals are preferably those containing 1 or 2hetero atoms, such as, for example, N, S and O. They are usuallysaturated. Heteroaryl radicals are usually aromatic heterocycles thatcontain preferably from 1 to 3 hetero atoms, such as N, S and/or O. Suchheterocycles and heteroaromatic radicals may furthermore be substituted,for example by halogen, C₁-C₄alkyl and/or amino. The C₂-C₂₀-alkenylgroups represented by R₃₁ may be mono- or poly-unsaturated. They containpreferably from 2 to 12, especially from 2 to 6, carbon atoms.

[0073] The definition of the electrophile G-L of formula XII includesthe following electrophiles: L-C(O)—R₃₀ (XIIa), L-C(X₁)—X₂—R₃₁ (XIIb),L-C(X₃)—N(R₃₂)—R₃₃ (XIIc), R₃₂N═C═X₃ (XIId), L-SO₂—R₃₄ (XIIe) andL-P(X₄)(R₃₅)—R₃₆ (XIIf).

[0074] In the electrophile of formula XII, L is a leaving group, suchas, for example, R₃OC(O)O— or R₃₁O— (wherein R₃₀ and R₃₁ are as definedfor formula Ia), or halogen, preferably chlorine, bromine or iodine.

[0075] The process according to the invention is especially well suitedto the preparation of compounds of formula I wherein R₀ is, eachindependently of any other, halogen, C₁-C₆alkyl, C₁-C₆haloalkyl,hydroxy, C₁-C₆alkoxy, nitro, amino, C₁-C₆alkylamino,di(C₁-C₆alkyl)amino, C₁-C₆alkylcarbonylamino, C₁-C₆alkylsulfonylamino,C₁-C₆alkylaminosulfonyl, C₁-C₄-alkylcarbonyl, C₁-C₆alkoxycarbonyl orcarboxy; and

[0076] R₁, R₂ and R₃ are each independently of the others hydrogen,halogen, C₁-C₆alkyl, C₂-C₆-alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl,C₁-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl,C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆alkylthio-C₁-C₆alkyl, cyano,C₁-C₄alkylcarbonyl, C₁-C₆alkoxycarbonyl, hydroxy, C₁-C₁₀alkoxy,C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C₁-C₆haloalkoxy, C₃-C₆haloalkenyloxy,C₁-C₆alkoxy-C₁-C₆alkoxy, mercapto, C₁-C₆alkylthio, C₁-C₆haloalkylthio,C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, nitro, amino, C₁-C₄alkylamino ordi(C₁-C₄alkyl)amino.

[0077] The process according to the invention is especially well suitedalso to the preparation of compounds of formula I wherein R₁, R₂ and R₃are each independently of the others hydrogen, halogen, C₁-C₄alkyl,C₂-C₄alkenyl, C₂-C₄alkynyl, C₁-C₄haloalkyl, C₃- or C₄-haloalkenyl,C₃-C₆cycloalkyl, C₁-C₄alkylcarbonyl, C₁-C₆alkoxycarbonyl, hydroxy,C₁-C₄alkoxy, C₃- or C₄-alkenyloxy, C₃- or C₄-alkynyloxy,C₁-C₄haloalkoxy, nitro or amino.

[0078] The process according to the invention is especially well suitedalso to the preparation of compounds of formula I wherein R₄ and R₅,together with the nitrogen atoms to which they are bonded, form asaturated or unsaturated, 6- or 7-membered heterocyclic ring that 1) maybe interrupted once by oxygen or by sulfur and/or 2) may contain a fusedor spiro-bound alkylene chain having from 2 to 5 carbon atoms that isoptionally interrupted once or twice by oxygen or by sulfur, or at leastone ring atom of the saturated or unsaturated heterocyclic ring bridgesthat alkylene chain.

[0079] In a preferred variant of the process according to the invention,there are preferably used compounds of formula II wherein R₈, R₉, R₁₀,R₁₁ and R₁₂ are hydrogen, C₁-C₆alkyl or benzyl.

[0080] The preparation of the compounds of formulae I and Ia isexplained in detail in the following Reaction Schemes 1 and 2.

[0081] The compounds of formulae II and IV, IVa or IVb can be used inequimolar amounts, but an excess of from 5 to 50 mol % of the compoundof formula IV, IVa or IVb can be of advantage.

[0082] The reaction of compounds of formula II with compounds of formulaIV, IVa or IVb is carried out at a reaction temperature of from 0° to200° C., a temperature range of from 80° C. to 150° C. being preferred.

[0083] Suitable inert organic solvents for the reaction of compounds offormula II with compounds of formula IV, IVa or IVb are, for example,aromatic, aliphatic and cycloaliphatic hydrocarbons, for example,benzene, toluene, the xylene isomers ortho-, meta- and para-xylene,cyclohexane and methylcyclohexane; halogenated hydrocarbons, for examplechlorobenzene and the dichlorobenzene isomers 1,2-, 1,3- and1,4-dichlorobenzene; ethers, for example dibutyl ether, tert-butylmethyl ether, 1,2-dimethoxyethane (DME), ethylene glycol dimethyl ether,diethylene glycol dimethyl ether, 1,3-dioxolane and dioxane; nitriles,for example acetonitrile, propionitrile and benzonitrile; dialkylsulfoxides, for example dimethyl sulfoxide (DMSO); amides and lactams,for example N,N-dimethylformamide (DMF), N,N-diethylformamide andN-methylpyrrolidone (NMP); alcohols, glycols (diols) and polyalcohols,for example propanol, butanol, cyclohexanol, ethylene glycol and2-ethoxyethanol, and also, generally, carboxylic acids, for exampleacetic acid and propionic acid, or mixtures of those solvents.

[0084] Preference is given to those organic solvents having a boilingpoint≧80° C., especially a boiling point≧100° C.

[0085] Special preference is given to toluene, the xylene isomersortho-, meta- and para-xylene, methylcyclohexane, chlorobenzene and thedichlorobenzene isomers 1,2-, 1,3- and 1,4-dichlorobenzene.

[0086] The reaction according to the invention is preferably carried outin an inert gas atmosphere, for example in a nitrogen or argon gasatmosphere.

[0087] The condensation of compounds of formula II with compounds offormula IV can be carried out with or without the addition of a base.The same condensation reaction carried out with compounds of formula IVaor IVb (instead of compounds of formula IV) is advantageously carriedout in the presence of a base. Suitable bases in that case include, forexample, nitrogen bases generally, for example tertiary amines andpyridines, for example C₁-C₆-trialkylamines, quinuclidine and4-dimethylaminopyridine. Further suitable bases are, for example, alkalimetal alcoholates, for example sodium and potassium methanolate, sodiumand potassium ethanolate and sodium and potassium tert-butanolate. It isalso possible to use inorganic bases, for example alkali metal andalkaline earth metal hydrides, such as sodium, potassium or calciumhydride, hydroxides, such as sodium or potassium hydroxide, carbonates,such as sodium or potassium carbonate, and hydrogen carbonates, such assodium or potassium hydrogen carbonate, especially in the form ofsolutions in alcohol. Such bases are used in catalytic amounts or in amolar excess of up to 5 based on the compound of formula II.

[0088] In a preferred embodiment of the process according to theinvention, an aromatic hydrocarbon having a boiling point>80° C., forexample xylene, is used as the reaction medium in which the reactants offormulae II and IV, IVa or IVb are dissolved. Preferably, the compoundof formula IV, IVa or IVb is used in an excess of from 5 to 20 mol %based on the compound of formula II. The reaction mixture is heated atreflux temperature for from 1 to 3 hours in an inert gas atmosphere,with or without the addition of a base when a compound of formula IV isused, and in the presence of an equimolar amount or an up to 5-foldexcess of an organic base, such as triethylamine, when a compound offormula IVa or IVb is used. After cooling and the addition of diluteacid, the desired product (G=hydrogen) precipitates in the form of acrystalline solid and can be filtered off directly and washed with asuitable washing agent, for example water and/or hexane.

[0089] The compounds of formula I wherein R₀, R₁, R₂, R₃, R₄, R₅ and nare as defined hereinbefore and G is hydrogen, a metal ion equivalent oran ammonium cation can readily be converted into the compounds offormula Ia either

[0090] a) in accordance with the invention, directly in the reactionsolution in a one-pot reaction, without isolation, or

[0091] b) in a subsequent reaction step, after having been isolated,

[0092] by means of reaction, optionally in the presence of anacid-binding agent or a catalyst, with an electrophile of formula XIIwherein G₀ is as defined hereinbefore and L is a leaving group, forexample R₃₀C(O)O— or R₃₁O— (wherein R₃₀ and R₃₁ are as defined forformula Ia), or halogen, preferably chlorine, bromine or iodine.Reaction Scheme 2 illustrates that derivatisation step.

[0093] The acid-binding agents that may be used for the reaction of acompound of formula I with an electrophile of formula XII may beconventional proton acceptors, for example alkali metal hydrides, alkalimetal alcoholates, alkali metal or alkaline earth metal carbonates orhydrogen carbonates, or nitrogen bases generally, for exampletriethylamine, diisopropylamine, pyridine, quinoline, diazabicyclononene(DBN) and diazabicycloundecene (DBU). There may be added as catalystsfor the reaction of a compound of formula I with an electrophile offormula IId catalysts that accelerate the reaction, for exampleorganotin compounds, for example dibutyltin dilaurate.

[0094] The solvents used may be any that are inert with respect to theelectrophiles of formulae XII and XIIa to XIIf, for example aromatichydrocarbons, for example benzene, toluene or a xylene isomer;halogenated hydrocarbons, for example dichloromethane, trichloromethane,chlorobenzene or a dichlorobenzene isomer; amides, for exampleN,N-dimethylformamide (DMF) or 1-methyl-2-pyrrolidone (NMP); or ethers,for example dibutyl ether, 1,2-dimethoxyethane (DME), 1,3-dioxolane,tetrahydrofuran or dioxane.

[0095] Analogous reactions of compounds of formula I wherein G ishydrogen in accordance with the above variant b), that is to say, as aseparate reaction step, are described, for example, in WO 97/02243 andEP-A-0 508 126.

[0096] The compounds of formula I prepared in accordance with theinvention wherein G is hydrogen, a metal ion equivalent or an ammonium,sulfonium or phosphonium cation are therefore used especially asstarting compounds for the ‘in situ’ preparation of compounds of formulaIa wherein G₀ is a group —C(O)—R₃₀, —C(X₁)—X₂—R₃₁, —C(X₃)—N(R₃₂)—R₃₃,—SO₂—R₃₄ or —P(X₄)(R₃₅)—R₃₆; and R₃₀, R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆, X₁,X₂, X₃ and X₄ are as defined for formula Ia.

[0097] The compounds of formula I

[0098] wherein R₀ is, each independently of any other, halogen,C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆-alkynyl, C₁-C₆haloalkyl,cyano-C₁-C₆alkyl, C₂-C₆haloalkenyl, cyano-C₂-C₆alkenyl,C₂-C₆haloalkynyl, cyano-C₂-C₆alkynyl, hydroxy, hydroxy-C₁-C₆alkyl,C₁-C₆alkoxy, nitro, amino, C₁-C₆-alkylamino, di(C₁-C₆alkyl)amino,C₁-C₆alkylcarbonylamino, C₁-C₆alkylsulfonylamino,C₁-C₆-alkylaminosulfonyl, C₁-C₆alkylcarbonyl,C₁-C₆alkylcarbonyl-C₁-C₆alkyl, C₁-C₆alkoxycarbonyl-C₁-C₆alkyl,C₁-C₆alkylcarbonyl-C₂-C₆alkenyl, C₁-C₆alkoxycarbonyl-C₂-C₆alkenyl,C1-C₆-alkylcarbonyl-C₂-C₆alkynyl, C₁-C₆alkoxycarbonyl-C₂-C₆alkynyl,C₁-C₆alkoxycarbonyl, cyano, carboxyl, phenyl or an aromatic ring thatcontains 1 or 2 hetero atoms selected from the group consisting ofnitrogen, oxygen and sulfur, wherein the latter two aromatic rings maybe substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,C₁-C₃haloalkoxy, halogen, cyano or by nitro; or R₀, together with theadjacent substituents R₁, R₂ and R₃, forms a saturated or unsaturatedC₃-C₆hydrocarbon bridge that may be interrupted by 1 or 2 hetero atomsselected from the group consisting of nitrogen, oxygen and sulfur and/ormay be substituted by C₁-C₄alkyl; R₁, R₂ and R₃ are each independentlyof the others hydrogen, halogen, C₁-C₆-alkyl, C₂-C₆alkenyl,C₂-C₆alkynyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl,C₁-C₆-alkoxycarbonyl-C₂-C₆alkenyl, C₁-C₆alkylcarbonyl-C₂-C₆alkenyl,cyano-C₂-C₆alkenyl, nitro-C₂-C₆alkenyl, C₂-C₆haloalkynyl,C₁-C₆alkoxycarbonyl-C₂-C₆alkynyl, C₁-C₆alkylcarbonyl-C₂-C₆-alkynyl,cyano-C₂-C₆alkynyl, nitro-C₂-C₆alkynyl, C₃-C₆-halocycloalkyl,hydroxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆alkylthio-C₁-C₆alkyl,cyano, C₁-C₄alkylcarbonyl, C₁-C₆alkoxycarbonyl, hydroxy, C₁-C₁₀alkoxy,C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C₁-C₆haloalkoxy, C₃-C₆haloalkenyloxy,C₁-C₆alkoxy-C₁-C₆alkoxy, mercapto, C₁-C₆alkylthio, C₁-C₆haloalkylthio,C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, nitro, amino, C₁-C₆alkylamino,di(C₁-C₆alkyl)-amino or phenoxy in which the phenyl ring may besubstituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy,halogen, cyano or by nitro;

[0099] R₂ also may be phenyl, naphthyl or a 5- or 6-membered aromaticring that may contain 1 or 2 hetero atoms selected from the groupconsisting of nitrogen, oxygen and sulfur, wherein the phenyl ring, thenaphthyl ring system and the 5- or 6-membered aromatic ring may besubstituted by halogen, C₃-C₈cycloalkyl, hydroxy, mercapto, amino,cyano, nitro or by formyl; and/or

[0100] the phenyl ring, the naphthyl ring system and the 5- or6-membered aromatic ring may be substituted by C₁-C₆alkyl, C₁-C₆alkoxy,hydroxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆-alkoxy-C₁-C₆alkoxy,C₁-C₆alkylcarbonyl, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl,C₁-C₆alkylsulfonyl, mono-C₁-C₆alkylamino, di(C₁-C₆alkyl)amino,C₁-C₆alkylcarbonylamino, C₁-C₆alkylcarbonyl-(C₁-C₆alkyl)amino,C₂-C₆alkenyl, C₃-C₆alkenyloxy, hydroxy-C₃-C₆alkenyl,C₁-C₆alkoxy-C₂-C₆alkenyl, C₁-C₆alkoxy-C₃-C₆alkenyloxy,C₂-C₆alkenylcarbonyl, C₂-C₆alkenylthio, C₂-C₆-alkenylsulfinyl,C₂-C₆alkenylsulfonyl, mono- or di-(C₂-C₆alkenyl)amino,C₁-C₆alkyl(C₃-C₆-alkenyl)amino, C₂-C₆alkenylcarbonylamino,C₂-C₆alkenylcarbonyl(C₁-C₆alkyl)amino, C₂-C₆-alkynyl, C₃-C₆alkynyloxy,hydroxy-C₃-C₆alkynyl, C₁-C₆alkoxy-C₃-C₆alkynyl,C₁-C₆alkoxy-C₄-C₆alkynyloxy, C₂-C₆alkynylcarbonyl, C₂-C₆alkynylthio,C₂-C₆alkynylsulfinyl, C₂-C₆alkynylsulfonyl, mono- ordi-(C₃-C₆alkynyl)amino, C₁-C₆alkyl(C₃-C₆alkynyl)amino,C₂-C₆alkynylcarbonylamino or by C₂-C₆alkynylcarbonyl(C₁-C₆alkyl)amino;and/or

[0101] the phenyl ring, the naphthyl ring system and the 5- or6-membered aromatic ring may be substituted by halo-substitutedC₁-C₆alkyl, C₁-C₆alkoxy, hydroxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl,C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆alkylcarbonyl, C₁-C₆alkylthio,C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, mono-C₁-C₆alkylamino,di(C₁-C₆alkyl)amino, C₁-C₆alkylcarbonylamino,C₁-C₆alkylcarbonyl(C₁-C₆alkyl)amino, C₂-C₆alkenyl, C₃-C₆alkenyloxy,hydroxy-C₃-C₆alkenyl, C₁-C₆alkoxy-C₂-C₆alkenyl,C₁-C₆alkoxy-C₃-C₆alkenyloxy, C₂-C₆alkenylcarbonyl, C₂-C₆alkenylthio,C₂-C₆alkenylsulfinyl, C₂-C₆alkenylsulfonyl, mono- ordi-(C₂-C₆alkenyl)amino, C₁-C₆alkyl-(C₃-C₆alkenyl)amino,C₂-C₆alkenylcarbonylamino, C₂-C₆alkenylcarbonyl(C₁-C₆alkyl)amino,C₂-C₆alkynyl, C₃-C₆alkynyloxy, hydroxy-C₃-C₆alkynyl,C₁-C₆alkoxy-C₃-C₆alkynyl, C₁-C₆alkoxy-C₄-C₆alkynyloxy,C₂-C₆alkynylcarbonyl, C₂-C₆alkynylthio, C₂-C₆alkynylsulfinyl,C₂-C₆alkynylsulfonyl, mono- or di-(C₃-C₆alkynyl)amino,C₁-C₆alkyl(C₃-C₆alkynyl)amino, C₂-C₆alkynylcarbonylamino orC₂-C₆alkynylcarbonyl(C₁-C₆alkyl)amino; and/or

[0102] the phenyl ring, the naphthyl ring system and the 5- or6-membered aromatic ring may be substituted by a radical of the formulaCOOR₅₀, CONR₅₁, SO₂NR₅₃R₄ or SO₂OR₅₅ wherein R₅₀, R₅₁, R₅₂, R₅₃, R₅₄ andR₅₅ are each independently of the others C₁-C₆alkyl, C₂-C₆alkenyl orC₃-C₆alkynyl or halo-, hydroxy-, alkoxy-, mercapto-, amino-, cyano-,nitro-, alkylthio-, alkylsulfinyl- or alkylsulfonyl-substitutedC₁-C₆alkyl, C₂-C₆alkenyl or C₃-C₆alkynyl; n is 1 or 2; R₄ and R₅,together with the nitrogen atoms to which they are bonded, form asaturated or unsaturated 5- to 8-membered heterocyclic ring that 1) isinterrupted by oxygen, sulfur or by —NR₁₄— and may be substituted byhalogen, C₁-C₁₀alkyl, C₁-C₁₀haloalkyl, hydroxy, C₁-C₆-alkoxy,C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆haloalkoxy, mercapto, C₁-C₆alkylthio,C₃-C₇cycloalkyl, heteroaryl, heteroaryl-C₁-C₆alkyl, phenyl,phenyl-C₁-C₆alkyl or by benzyloxy, wherein the phenyl rings of the lastthree substituents may in turn be substituted by halogen, C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy or by nitro, and 2) maycontain a fused or spiro-bound alkylene or alkenylene chain having from2 to 6 carbon atoms that is optionally interrupted by oxygen or bysulfur, or at least one ring atom of the saturated or unsaturatedheterocyclic ring bridges that alkylene or alkenylene chain; R₁₄ ishydrogen, C₁-C₄alkyl, C₁-C₆alkylcarbonyl, C₁-C₆alkylsulfonyl,C₃-C₆alkenyl or C₃-C₆alkynyl; and G is hydrogen or a metal ionequivalent or an ammonium, sulfonium or phosphonium cation, are new. Thepresent invention accordingly relates also to those compounds.

[0103] The compounds of formula Ia

[0104] wherein R₀ is, each independently of any other, halogen,C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆-alkynyl, C₁-C₆haloalkyl,cyano-C₁-C₆alkyl, C₂-C₆haloalkenyl, cyano-C₂-C₆alkenyl,C₂-C₆haloalkynyl, cyano-C₂-C₆alkynyl, hydroxy, hydroxy-C₁-C₆alkyl,C₁-C₆alkoxy, nitro, amino, C₁-C₆alkylamino, di(C₁-C₆alkyl)amino,C₁-C₆alkylcarbonylamino, C₁-C₆alkylsulfonylamino,C₁-C₆alkylaminosulfonyl, C₁-C₆alkylcarbonyl,C₁-C₆alkylcarbonyl-C₁-C₆alkyl, C₁-C₆alkoxycarbonyl-C₁-C₆alkyl,C₁-C₆alkylcarbonyl-C₂-C₆alkenyl, C₁-C₆alkoxycarbonyl-C₂-C₆-alkenyl,C₁-C₆alkylcarbonyl-C₂-C₆alkynyl, C₁-C₆alkoxycarbonyl-C₂-C₆alkynyl,C₁-C₆-alkoxycarbonyl, cyano, carboxyl, phenyl or an aromatic ring thatcontains 1 or 2 hetero atoms selected from the group consisting ofnitrogen, oxygen and sulfur, wherein the latter two aromatic rings maybe substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,C₁-C₃-haloalkoxy, halogen, cyano or by nitro; or R₀, together with theadjacent substituents R₁, R₂ and R₃, forms a saturated or unsaturatedC₃-C₆hydrocarbon bridge that may be interrupted by 1 or 2 hetero atomsselected from the group consisting of nitrogen, oxygen and sulfur and/ormay be substituted by C₁-C₄alkyl; R₁, R₂ and R₃ are each independentlyof the others hydrogen, halogen, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl,C₃-C₆cycloalkyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl,C₁-C₆alkoxycarbonyl-C₂-C₆alkenyl, C₁-C₆alkylcarbonyl-C₂-C₆alkenyl,cyano-C₂-C₆alkenyl, nitro-C₂-C₆alkenyl, C₂-C₆haloalkynyl,C₁-C₆alkoxycarbonyl-C₂-C₆alkynyl, C₁-C₆alkylcarbonyl-C₂-C₆alkynyl,cyano-C₂-C₆alkynyl, nitro-C₂-C₆alkynyl, C₃-C₆halocycloalkyl,hydroxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆alkylthio-C₁-C₆alkyl,cyano, C₁-C₄alkylcarbonyl, C₁-C₆alkoxycarbonyl, hydroxy, C₁-C₁₀alkoxy,C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C₁-C₆haloalkoxy, C₃-C₆haloalkenyloxy,C₁-C₆alkoxy-C₁-C₆alkoxy, mercapto, C₁-C₆alkylthio, C₁-C₆haloalkylthio,C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, nitro, amino, C₁-C₆alkylamino,di-(C₁-C₆alkyl)amino or phenoxy in which the phenyl ring may besubstituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy,halogen, cyano or by nitro;

[0105] R₂ also may be phenyl, naphthyl or a 5- or 6-membered aromaticring that may contain 1 or 2 hetero atoms selected from the groupconsisting of nitrogen, oxygen and sulfur, wherein the phenyl ring, thenaphthyl ring system and the 5- or 6-membered aromatic ring may besubstituted by halogen, C₃-C₈cycloalkyl, hydroxy, mercapto, amino,cyano, nitro or by formyl; and/or

[0106] the phenyl ring, the naphthyl ring system and the 5- or6-membered aromatic ring may be substituted by C₁-C₆alkyl, C₁-C₆alkoxy,hydroxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆-alkoxy-C₁-C₆alkoxy,C₁-C₆alkylcarbonyl, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl,C₁-C₆alkylsulfonyl, mono-C₁-C₆alkylamino, di(C₁-C₆alkyl)amino,C₁-C₆alkylcarbonylamino, C₁-C₆alkylcarbonyl-(C₁-C₆alkyl)amino,C₂-C₆alkenyl, C₃-C₆alkenyloxy, hydroxy-C₃-C₆alkenyl,C₁-C₆alkoxy-C₂-C₆-alkenyl, C₁-C₆alkoxy-C₃-C₆alkenyloxy,C₂-C₆alkenylcarbonyl, C₂-C₆alkenylthio, C₂-C₆alkenylsulfinyl,C₂-C₆alkenylsulfonyl, mono- or di-(C₂-C₆alkenyl)amino,C₁-C₆alkyl(C₃-C₆alkenyl)-amino, C₂-C₆alkenylcarbonylamino,C₂-C₆alkenylcarbonyl(C₁-C₆alkyl)amino, C₂-C₆alkynyl, C₃-C₆alkynyloxy,hydroxy-C₃-C₆alkynyl, C₁-C₆alkoxy-C₃-C₆alkynyl,C₁-C₆alkoxy-C₄-C₆alkynyloxy, C₂-C₆alkynylcarbonyl, C₂-C₆alkynylthio,C₂-C₆alkynylsulfinyl, C₂-C₆alkynylsulfonyl, mono- ordi-(C₃-C₆alkynyl)amino, C₁-C₆alkyl(C₃-C₆alkynyl)amino,C₂-C₆alkynylcarbonylamino or by C₂-C₆alkynylcarbonyl(C₁-C₆alkyl)amino;and/or

[0107] the phenyl ring, the naphthyl ring system and the 5- or6-membered aromatic ring may be substituted by halo-substitutedC₁-C₆alkyl, C₁-C₆alkoxy, hydroxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl,C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆alkylcarbonyl, C₁-C₆alkylthio,C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, mono-C₁-C₆alkylamino,di(C₁-C₆alkyl)amino, C₁-C₆alkylcarbonylamino,C₁-C₆alkylcarbonyl(C₁-C₆alkyl)amino, C₂-C₆alkenyl, C₃-C₆alkenyloxy,hydroxy-C₃-C₆alkenyl, C₁-C₆alkoxy-C₂-C₆alkenyl,C₁-C₆alkoxy-C₃-C₆alkenyloxy, C₂-C₆alkenylcarbonyl, C₂-C₆alkenylthio,C₂-C₆alkenylsulfinyl, C₂-C₆alkenylsulfonyl, mono- ordi-(C₂-C₆alkenyl)amino, C₁-C₆alkyl-(C₃-C₆alkenyl)amino,C₂-C₆alkenylcarbonylamino, C₂-C₆alkenylcarbonyl(C₁-C₆alkyl)amino,C₂-C₆alkynyl, C₃-C₆alkynyloxy, hydroxy-C₃-C₆alkynyl,C₁-C₆alkoxy-C₃-C₆alkynyl, C₁-C₆alkoxy-C₄-C₆alkynyloxy,C₂-C₆alkynylcarbonyl, C₂-C₆alkynylthio, C₂-C₆alkynylsulfinyl,C₂-C₆alkynylsulfonyl, mono- or di-(C₃-C₆alkynyl)amino,C₁-C₆alkyl(C₃-C₆alkynyl)amino, C₂-C₆alkynylcarbonylamino orC₂-C₆alkynylcarbonyl(C₁-C₆alkyl)amino; and/or

[0108] the phenyl ring, the naphthyl ring system and the 5- or6-membered aromatic ring may be substituted by a radical of the formulaCOOR₅₀, CONR₅₁, SO₂NR₅₃R₅₄ or SO₂OR₅₅ wherein R₅₀, R₅₁, R₅₂, R₅₃, R₅ andR₅₅ are each independently of the others C₁-C₆alkyl, C₂-C₆alkenyl orC₃-C₆alkynyl or halo-, hydroxy-, alkoxy-, mercapto-, amino-, cyano-,nitro-, alkylthio-, alkylsulfinyl- or alkylsulfonyl-substitutedC₁-C₆alkyl, C₂-C₆alkenyl or C₃-C₆alkynyl;

[0109] n is 1 or 2;

[0110] R₄ and R₅, together with the nitrogen atoms to which they arebonded, form a saturated or unsaturated 5- to 8-membered heterocyclicring that 1) is interrupted by oxygen, sulfur or by —NR₁₄— and may besubstituted by halogen, C₁-C₁₀alkyl, C₁-C₁₀haloalkyl, hydroxy,C₁-C₆-alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆haloalkoxy, mercapto,C₁-C₆alkylthio, C₃-C₇cycloalkyl, heteroaryl, heteroaryl-C₁-C₆alkyl,phenyl, phenyl-C₁-C₆alkyl or by benzyloxy, wherein the phenyl rings ofthe last three substituents may in turn by substituted by halogen,C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy or by nitro,and 2) may contain afused or spiro-bound alkylene or alkenylene chainhaving from 2 to 6 carbon atoms that is optionally interrupted by oxygenor by sulfur, or at least one ring atom of the saturated or unsaturatedheterocyclic ring bridges that alkylene or alkenylene chain; R₁₄ ishydrogen, C₁-C₄alkyl, C₁-C₆alkylcarbonyl, C₁-C₆alkylsulfonyl,C₃-C₆alkenyl or C₃-C₆alkynyl; and Go is a group —C(O)—R₃₀, —C(X₁)—X₂—R₃₁or —SO₂—R₃₄;

[0111] X₁, X₂, X₃ and X₄ are each independently of the others oxygen orsulfur;

[0112] R₃₀ is unsubstituted or halo-substituted C₁-C₂₀alkyl,C₂-C₂₀alkenyl, C₁-C₈alkoxy-C₁-C₈alkyl, C₁-C₈alkylthio-C₁-C₈alkyl,poly-C₁-C₈alkoxy-C₁-C₈alkyl or unsubstituted or halo-substitutedC₃-C₈cycloalkyl, C₃-C₆cycloalkyl-C₁-C₆alkyl, heterocyclyl-C₁-C₆alkyl,heteroaryl-C₁-C₆alkyl, unsubstituted or halo-, cyano-, nitro-,C₁-C₆alkyl-, C₁-C₆alkoxy-, C₁-C₆haloalkyl-, C₁-C₆haloalkoxy-,C₁-C₆alkylthio- or C₁-C₆alkylsulfonyl-substituted phenyl, unsubstitutedor halo-, nitro-, cyano-, C₁-C₆alkyl-, C₁-C₆alkoxy-, C₁-C₆haloalkyl- orC₁-C₆haloalkoxy-substituted phenyl-C₁-C₆alkyl, unsubstituted or halo- orC₁-C₆alkyl-substituted heteroaryl, unsubstituted or halo- orC₁-C₆alkyl-substituted phenoxy-C₁-C₆alkyl, or unsubstituted or halo-,amino- or C₁-C₆alkyl-substituted heteroaryloxy-C₁-C₆alkyl; R₃₁ isunsubstituted or halo-substituted C₁-C₂₀alkyl, C₂-C₂₀alkenyl,C₁-C₈alkoxy-C₂-C₈alkyl, poly-C₁-C₈alkoxy-C₂-C₈alkyl, unsubstituted orhalo- or C₁-C₆alkoxy-substituted C₃-C₈cycloalkyl,C₃-C₆cycloalkyl-C₁-C₆alkyl, heterocyclyl-C₁-C₆alkyl,heteroaryl-C₁-C₆alkyl, unsubstituted or halo-, cyano-, nitro-,C₁-C₆-alkyl-, C₁-C₆alkoxy-, C₁-C₆haloalkyl- orC₁-C₆haloalkoxy-substituted phenyl or benzyl; and R₃₄ is unsubstitutedor halo-substituted C₁-C₈alkyl, or unsubstituted or halo-, C₁-C₆alkyl-,C₁-C₆-alkoxy-, C₁-C₄haloalkyl-, C₁-C₄haloalkoxy-, cyano- ornitro-substituted phenyl, are new. The present invention accordinglyrelates also to those compounds.

[0113] The compounds of formula II

[0114] wherein R₀, R₁, R₂, R₃, R₆, R₇ and n are as defined hereinbeforeare new and were developed especially for the process according to theinvention. The present invention accordingly relates also to thosecompounds.

[0115] Preferred compounds of formula II are those wherein R₁, R₂ and R₃are each independently of the others hydrogen, halogen, C₁-C₄alkyl,C₁-C₄haloalkyl, C₂-C₄alkenyl, C₂-C₄haloalkenyl, C₂-C₄alkynyl,C₃-C₆cycloalkyl, C₁-C₄alkylcarbonyl, C₁-C₆alkoxycarbonyl, hydroxy,C₁-C₄-alkoxy, C₃— or C₄-alkenyloxy, C₃— or C₄-alkynyloxy,C₁-C₄haloalkoxy, nitro or amino.

[0116] Preference is given also to compounds of formula II wherein R₁ isC₂-C₆alkyl.

[0117] Likewise preferred are compounds of formula II wherein n is 0.

[0118] Of those, special preference is given to compounds of formula IIwherein R₁ is C₂-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkynyl or C₃-C₆cycloalkyland R₃ is C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkynyl or C₃-C₆cycloalkyl.

[0119] Likewise preferred are compounds of formula II wherein R₁ isC₂-C₆alkynyl.

[0120] Preference is given to those compounds of formula II wherein R₁and R₃ are each independently of the other C₂-C₆alkyl, C₂-C₆alkynyl,C₁-C₁₀alkoxy or C₃-C₆cycloalkyl. Of those, special preference is givento the compounds wherein R₁ is C₂-C₆alkyl and R₃ is C₂-C₆alkyl,C₂-C₆alkynyl or C₁-C₁₀alkoxy.

[0121] Also important are the compounds of formula II wherein R₆ isR₈R₉N— and R₇ is R₁₀R₁₁N—; R₈, R₉, R₁₀ and R₁₁ being as defined forformula II.

[0122] The compounds of formula IIa

[0123] wherein R₀, R₁, R₂, R₃ and n are as defined for formula I and R₈,R₉, R₁₀ and R₁₁ are hydrogen, can be obtained, for example, directlyfrom the corresponding phenylmalonic acid dinitriles of formula VI

[0124] wherein R₀, R₁, R₂, R₃ and n are as defined hereinbefore, bymeans of hydrolysis. Concentrated mineral acids, for example, sulfuricacid or nitric acid, are suitable as hydrolysing agents, whereappropriate with the addition of water.

[0125] The compounds of formula IIa

[0126] wherein R₀, R₁, R₂, R₃ and n are as defined for formula I and R₈,R₉, R₁₀ and R₁₁, are each independently of the others hydrogen,C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl or benzyl, wherein the phenylring of the benzyl group may be substituted by C₁-C₄alkyl, halogen,C₁-C₄haloalkyl, C₁-C₄alkoxy or by nitro, can be prepared, for example,as follows:

[0127] 1) a phenyl acetamide of formula VII

[0128] wherein R₀, R₁, R₂, R₃, R₈, R₉ and n are as defined hereinbefore,is either

[0129] a) reacted with an isocyanate of formula XI

R₁₀N═C═O  (XI),

[0130] wherein R₁₀ is as defined hereinbefore except that R₁₀ is nothydrogen, the reaction being optionally catalysed by a base and carriedout in an inert reaction medium, (R₁₁=hydrogen in the compound offormula IIa), or

[0131] b) reacted at reflux temperature with a carbonate of formula XIV

[0132] wherein R₁₂ is C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl orbenzyl, wherein the phenyl ring of the benzyl group may be substitutedby C₁-C₄alkyl, halogen, C₁-C₄haloalkyl, C₁-C₄alkoxy or by nitro, and thecompound of formula IIb

[0133] wherein R₀, R₁, R₂, R₃, R₈, R₉, R₁₂ and n are as definedhereinbefore, is obtained initially and that compound is then reacted inan inert solvent with an amine of formula X

R₁₀R₁₁NH  (X),

[0134] wherein R₁₀ and R₁₁, are as defined hereinbefore, or

[0135] 2) a phenylacetic acid ester of formula VIII

[0136] wherein R₀, R₁, R₂, R₃, R₁₂ and n are as defined hereinbefore, iseither

[0137] c) reacted with an isocyanate of formula XV

R₈N═C═O  (XV),

[0138] wherein R₈ is as defined hereinbefore except that R₈ is nothydrogen, the reaction being optionally catalysed by a base and carriedout in an inert reaction medium, and the compound of formula IIb

[0139] wherein R₀, R₁, R₂, R₃, R₈, R₁₂ and n are as defined hereinbeforeand R₉ is hydrogen, is obtained initially, and that compound is thenreacted in an inert solvent, in the manner described under 1) b), withan amine of formula X, or

[0140] d) reacted with a carbonate of formula XVI

[0141] wherein R₁₃ has the same meanings as R₁₂, at elevatedtemperature, and a phenylmalonic acid diester of formula III

[0142] wherein R₀, R₁, R₂, R₃, R₁₂, R₁₃ and n are as definedhereinbefore, is obtained initially and that compound is then reacted inan inert solvent, in a manner analogous to that described under 1) b),with an amine of formula IX or X

R₈R₉NH  (IX)

or

R₁₀R₁₁NH  (X),

[0143] wherein R₈, R₉, R₁₀ and R₁₁ are as defined hereinbefore.

[0144] The above process variants are illustrated in the followingReaction Scheme 3.

[0145] The phenylmalonic acid diamides of formula IIa can be obtained inaccordance with Reaction Scheme 3 (variant a)), according to knownstandard procedures, from phenyl acetamides of formula VII using theisocyanates of formula XI, the reaction being optionally catalysed by abase and carried out in an inert solvent.

[0146] According to Reaction Scheme 3 (variant b)), the phenylmalonicacid diamides of formula IIa can be obtained from the phenyl acetamidesof formula VII also by heating for several hours at reflux temperaturein carbonates of formula XIV as solvents, via compounds of formula IIband with subsequent amidation in a solvent using amines of formula X.Analogous reactions with phenylacetic acid ester derivatives andcarbonates of formula XVI are described, for example, in WO 97/02243.

[0147] Further alternative processes for the preparation of thephenylmalonic acid diamides of formula IIa, which start from thephenylacetic acid esters of formula VIII, are provided according toReaction Scheme 3 by the following two process variants: according tovariant c), the compounds of formula VII can, for example, first of allbe reacted analogously to Tetrahedron Lett. 1974, 2427 with isocyanatesof formula XV, the reaction being catalysed by a base and carried out inan inert reaction medium, to form the compounds of formula IIb(R₉=hydrogen), which are then amidated in an inert solvent in a manneranalogous to variant b) using amines of formula X; or, according tovariant d), the compounds of formula VII can, for example, first of allbe reacted at reflux temperature, in carbonates of formula XVI assolvents, to form the phenylmalonic acid diesters of formula III, whichare then amidated in a solvent in a manner analogous to variant b) usingamines of formula IX or X.

[0148] The compounds of formulae IV, IVa and IVb are either known or canbe prepared analogously to known procedures. Processes for thepreparation of compounds of formula IV are described, for example, in WO95/00521 and PCT/EP Application number 99/01593.

[0149] The phenylmalonic acid dinitrile derivatives of formula VI areeither known or can be prepared analogously to known procedures asdescribed, for example, in Chem. Commun. 1984, 932 or J. Am. Chem. Soc.121, 1473 (1999).

[0150] The phenyl acetamides and phenylacetic acid esters of formulaeVII and VII are known. Phenylacetic acid esters of formula VII aredescribed, for example, in WO 97/02243.

[0151] The reagents of formulae IX, X, XI, XII and XIIa, XIIb, XIIc,XIId, XIIe and XIIf, XIV, XV and XVI used in Reaction Schemes 1, 2 and3, respectively, are either known or can be prepared analogously toknown procedures.

[0152] The present process is distinguished by:

[0153] a) easy accessibility of the starting compounds of formula II,

[0154] b) simple reaction procedure and working up,

[0155] c) generally high product yields,

[0156] d) an economically and ecologically advantageous one-pot processfor further derivatisation of the compounds of formula I to producecompounds of formula Ia (e.g. conversion of substituent G to G₀), and

[0157] e) its economic and ecological advantages derived from the factthat the individual process steps, starting from the preparation of thecompounds of formula II (Reaction Scheme 3), the reaction thereof withcompounds of formula IV, IVa or IVb to form compounds of formula I(Reaction Scheme 1) and the reaction thereof with electrophiles offormula XII, XIIa, XIIb, XIIc or XIId, can be used for a continuousreaction procedure for the preparation of compounds of formula Ia.

[0158] The present preparation process is suitable also especially forthe large-scale preparation of 4-aryl-5-oxopyrazoline derivatives offormulae I and Ia.

[0159] The Examples that follow further illustrate the process accordingto the invention without limiting it.

PREPARATION EXAMPLES Example P1 Preparation of2,4,6-trimethylphenylmalonic acid diamide

[0160]

[0161] A solution of 2.0 g (0.0109 mol) of 2,4,6-trimethylphenylmalonicacid dinitrile in 5 ml of dichloromethane is added dropwise within aperiod of 2 minutes to a mixture of 5 ml of concentrated sulfuric acid(97%) and 0.4 ml (0.022 mol) of water. After stirring for 100 hours at20° C., the reaction mixture is poured onto ice and extracted twice withethyl acetate. The combined organic phases are washed with saturatedsodium chloride solution, dried over sodium sulfate and concentrated invacuo at 60° C. 2.0 g (83% of theory) of the desired title compound areobtained in the form of yellowish crystals, m.p. 177-179° C.

Example P2 Preparation of 2,6-diethyl-4-methylphenylmalonic acid diamide

[0162]

[0163] 2.1 g (0.0099 mol) of 2,6-diethyl-4-methylphenylmalonic aciddinitrile are added to a mixture of 5 ml of concentrated sulfuric acid(97%) and 0.36 ml (0.0198 mol) of water. After stirring for 5 minutes at50° C., a homogeneous red-coloured solution forms which is furtherstirred for 5 hours at 50° C. The reaction mixture is then cooled to 22°C. and subsequently poured into ice-water. After extraction twice withethyl acetate, the combined organic phases are washed with saturatedsodium chloride solution, dried over sodium sulfate and concentrated invacuo at 60° C. 2.35 g (95.6% of theory) of the desired title compoundare obtained in the form of yellowish crystals, m.p. 184-186° C. ¹H-NMR(CDCl₃): 7.19 ppm (broad s, 1H); 6.99 ppm (s, 2H); 5.78 ppm (broad s,1H); 4.69 ppm (s, 1H); 2.55 ppm (q, 4H); 2.32 ppm (s, 3H); 1.21 ppm (t,6H).

Example P3 Preparation of8-(2,4,6-trimethylphenyl)tetrahydropyrazolo[1,2-d][1,4,5]oxadiazepine-7,9-dione

[0164]

[0165] A solution of 1.5 g (0.0068 mol) of 2,4,6-trimethylphenylmalonicacid diamide, 2.16 g (0.0082 mol) of [1,4,5]oxadiazepane dihydrobromideand 2.93 g (0.029 mol) of triethylamine in 50 ml of xylene is heated fortwo hours at reflux temperature in a nitrogen atmosphere. The suspensionformed is cooled to 22° C., stirred with 1N hydrochloric acid andfiltered. The crystalline residue is washed with water and then withdiethyl ether and dried in vacuo at 60° C. The desired title compoundhas a melting point of 248-250° C.

Example P4 Preparation of8-(2,6-diethyl-4-methylphenyl)tetrahydropyrazolo[1,2-d][1,4,5]-oxadiazepine-7,9-dione

[0166]

[0167] A solution of 2.15 g (0.00866 mol) of2,6-diethyl-4-methylphenylmalonic acid diamide, 2.64 g (0.010 mol) of[1,4,5]oxadiazepane dihydrobromide and 3.54 g (0.035 mol) oftriethylamine in 50 ml of xylene is heated for 2 hours at refluxtemperature in a nitrogen atmosphere. The resulting suspension is cooledto 22° C., 50 ml of 1N hydrochloric acid are added and the batch isstirred for 5 minutes. After the addition of 50 ml of hexane, theresulting solid is filtered off, washed with a small amount of water andhexane and dried in vacuo at 80° C. 2.15 g of the desired title compoundare obtained in the form of a colourless solid, m.p. 193-194° C. Theorganic phase is dried over sodium sulfate and concentrated in vacuo at60° C. to yield a further 0.23 g of the desired title compound. Totalyield 2.38 g (87% of theory). ¹H-NMR (CDCl₃): 6.92 ppm (d, 2H); 4.72 ppm(s, 1H); 4.30 ppm (m, 2H); 3.98 ppm (m, 4H); 3.79 ppm (m, 2H); 2.80 ppm(s, 3H); 2.70 ppm (q, 2H); 2.27 ppm (q, 2H); 1.27 ppm (t, 3H); 1.20 ppm(t, 3H).

Example P5 Preparation of8-(2,6-diethyl-4-methylphenyl)tetrahydropyrazolo[1,2-d][1,4,5]-oxadiazepine-7,9-dione

[0168]

[0169] A solution of 0.55 g (0.002 mol) of2-(2,6-diethyl-4-methylphenyl)-N,N′-dimethylmalonamide, 0.42 g (0.0024mol) of [1,4,5]oxadiazepane dihydrobromide and 1.17 ml (0.0084 mol) oftriethylamine in 6 ml of xylene is heated for 18 hours at refluxtemperature in a nitrogen atmosphere. The reaction mixture is thenpoured into water, the mixture is rendered acidic with 2N hydrochloricacid and the suspension is stirred with hexane. The solid is filteredoff, washed with water and hexane and dried in vacuo at 50° C. 0.33 g ofthe desired title compound is obtained in the form of beige crystals,m.p. 192-193.5° C.

Example P6 One-Pot Process for the Preparation of 2,2-dimethylipropionicacid8-(2,6-diethyl-4-methylphenyl)-9-oxo-1,2,4,5-tetrahydro-9H-pyrazolo[1,2-d][1,4,5]oxadiazepin-7-ylester

[0170]

[0171] A solution of 1.0 g (0.004 mol) of2,6-diethyl-4-methylphenylmalonic acid diamide, 0.84 g (0.0048 mol) of[1,4,5]oxadiazepane dihydrobromide and 1.62 g (0.016 mol) oftriethylamine in 25 ml of xylene is heated for 2 hours at refluxtemperature in a nitrogen atmosphere. The reaction mixture is thencooled to room temperature, 0.87 g (0.0072 mol) of pivaloyl chloride isadded and the batch is stirred for a further 2 hours at 22° C. Thereaction mixture is then stirred with 25 ml of 1N hydrochloric acid andextracted with ethyl acetate. The organic extracts are washed withsaturated sodium chloride solution, dried over sodium sulfate andconcentrated in vacuo at 60° C. 2.3 g of brown oil are obtained.Recrystallisation from hexane yields 1.0 g of the desired title compoundin the form of colourless crystals, m.p. 120-122° C.

[0172]¹H-NMR (CDCl₃): 6.89 ppm (s, 2H); 4.29 ppm (m, 2H); 3.95 ppm (m,2H); 3.87 ppm (m, 4H); 2.49 ppm (m, 4H); 2.30 ppm (s, 3H); 1.12 ppm (t,6H); 1.04 ppm (s, 9H).

Example P7 Preparation of2-(2,6-diethyl-4-methylphenyl)-N,N′-dimethylmalonamide

[0173]

[0174] 30 ml of a 33% solution of methylamine in ethanol are added to4.18 g (0.015 mol) of 2-(2,6-diethyl-4-methylphenyl)malonic aciddimethyl ester at 22° C. and the batch is stirred at 75° C. for 30hours. The reaction mixture is then poured into water, and the mixtureis rendered acidic with concentrated hydrochloric acid and extractedwith ether. The organic extracts are washed with saturated sodiumchloride solution, dried over magnesium sulfate and concentrated invacuo at 60° C. The residue obtained (4.0 g of a brown oil) is stirredwith hexane, 1.74 g of the desired title compound being obtained in theform of a crystalline product, m.p. 98-100° C.

Example P8 Preparation of2-(2,4,6-trimethylphenyl)tetrahydropyrazolo[1,2-a]pyridazine-1,3-dione(Without the Addition of a Base)

[0175]

[0176] A solution of 2.05 g (0.0093 mol) of 2,4,6-trimethylphenylmalonicacid diamide and 0.95 g (0.0110 mol) of hexahydropyridazine in 50 ml ofxylene is boiled for 2 hours at reflux temperature under nitrogen. Thereaction mixture is then cooled to 22° C. and stirred with 50 ml of 1Nhydrochloric acid; the resulting suspension is filtered and thecrystalline residue is washed first with diethyl ether and then withwater and dried in vacuo. 2.2 g of the desired title compound areobtained in the form of colourless crystals, m.p. 247-248° C.

[0177]¹H-NMR (CDCl₃): 6.93 ppm (s, 1H); 6.83 ppm (s, 1H); 4.65 ppm (s,1H); 3.67 ppm (broad s, 4H); 2.40 ppm (s, 3H); 2.27 ppm (s, 3H); 2.04ppm (s, 3H); 1.83 ppm (broad s, 4H).

Example P9 Preparation of 2,6-diethyl-4-(4-pyridyl)phenylmalonic aciddiamide

[0178]

[0179] 36 mg (0.002 mol) of water and then 360 mg (about 75%, 0.001 mol)of (2,6-diethyl-4-(4-pyridyl)phenylmalonic acid dinitrile are added to0.5 ml of sulfuric acid (97%) and the batch is stirred at 50° C. for 5.5hours. The cooled reaction mixture is neutralised with saturated sodiumhydrogen carbonate solution, the resulting precipitate is filtered offand washed with water, and the crystals are suspended with a smallamount of diethyl ether, filtered off and dried. The desired titlecompound is obtained in a yield of 145 mg (47% of theory), m.p. 184-186°C.

[0180]¹H-NMR (CDCl₃): 8.63 ppm (d, 2H); 7.48 ppm (d, 2H); 7.40 ppm (s,2H); 7.20 ppm (broad signal, 2H); 5.81 ppm (broad signal, 2H); 4.80 ppm(s, 1H); 2.68 ppm (q, 4H); 1.30 ppm (t, 6H).

[0181] The following compound (Example P10) is also obtained analogouslyto the above Example: 2,6-diethyl-4-(2-pyridyl)phenylmalonic aciddiamide, m.p. 230° C. (decomposition) and

[0182]¹H-NMR (CDCl₃): 8.68 ppm (d, 1H); 4.66-7.80 ppm (m, 4H); 7.23 ppm(m, 1H); 7.20 ppm (broad signal, 2H); 5.67 ppm (broad signal, 2H); 4.80ppm (s, 1H); 2.67 ppm (q, 4H); 1.30 ppm (t, 6H).

Example P11 Preparation of 2,2-dimethylpropionic acid8-(2,6-diethyl-2-pyridin-4-ylphenyl)-9-oxo-1,2,4,5-tetrahydro-9H-pyrazolo[1,2-d][1,4,5]oxadiazepin-7-ylester

[0183]

[0184] 290 mg (0.0011 mol) of [1,4,5]oxadiazepane dihydrobromide and0.56 ml (0.004 mol) of triethylamine are introduced into 7 ml ofdegassed xylene, 311 mg (0.001 mol) of2,6-diethyl-4-(2-pyridyl)phenylmalonic acid diamide are added, and thebatch is stirred at 150° C. for 4 hours. The reaction mixture is left tostand overnight at 20° C., is then cooled to from 0 to 5° C. and 0.135ml (0.0011 mol) of pivalic acid chloride is added dropwise. The batch isstirred for 3 hours at 20° C. to complete the reaction, poured intoice-water and extracted twice with ethyl acetate. The combined organicphases are washed with water and brine, dried over sodium sulfate andconcentrated. The crude product of 345 mg (75% of theory) iscrystallised from diethyl ether. The desired title compound is obtainedin a yield of 160 mg (35% of theory), m.p. 146-147° C.

[0185]¹H-NMR (CDCl₃): 8.70 ppm (m, 1H); 7.72 ppm (m, 2H); 7.70 ppm (s,2H); 7.22 ppm (m, 1H); 4.30 ppm (m, 2H); 3.97 ppm (m, 2H); 3.89 ppm (m,4H); 2.62 ppm (m, 4H); 1.21 ppm (t, 6H); 1.03 ppm (s, 9H).

[0186] The following compound (Example P12) is also obtained analogouslyto the above Example: 2,2-dimethylpropionic acid8-(2,6-diethyl-4-pyridin-4-ylphenyl)-9-oxo-1,2,4,5-tetrahydro-9.H.-pyrazolo[1,2-d][1,4,5]oxadiazepin-7-ylester, ¹H-NMR (CDCl₃): 8.19 ppm (broad signal, 2H); 7.53 ppm (broadsignal, 2H); 7.35 ppm (s, 2H); 4.30 ppm (m, 2H); 3.96 ppm (m, 2H); 3.89ppm (m, 4H); 2.62 ppm (m, 4H); 1.20 ppm (t, 6H); 1.05 ppm (s, 9H).

What is claimed is:
 1. A process for the preparation of a compound offormula I

wherein R₀ is, each independently of any other, halogen, C₁-C₆alkyl,C₂-C₆alkenyl, C₂-C₆alkynyl, C₁-C₆haloalkyl, cyano-C₁-C₆alkyl,C₂—C₆haloalkenyl, cyano-C₂-C₆alkenyl, C₂-C₆haloalkynyl,cyano-C₂-C₆alkynyl, hydroxy, hydroxy-C₁-C₆alkyl, C₁-C₆alkoxy, nitro,amino, C₁-C₆alkylamino, di(C₁-C₆alkyl)amino, C₁-C₆alkylcarbonylamino,C₁-C₆alkylsulfonylamino, C₁-C₆alkylaminosulfonyl, C₁-C₆alkylcarbonyl,C₁-C₆alkylcarbonyl-C₁-C₆alkyl, C₁-C₆alkoxycarbonyl-C₁-C₆alkyl,C₁-C₆alkylcarbonyl-C₂-C₆alkenyl, C₁-C₆alkoxycarbonyl-C₂-C₆alkenyl,C₁-C₆alkylcarbonyl-C₂-C₆alkynyl, C₁-C₆alkoxycarbonyl-C₂-C₆alkynyl,C₁-C₆alkoxycarbonyl, cyano, carboxyl, phenyl or an aromatic ring thatcontains 1 or 2 hetero atoms selected from the group consisting ofnitrogen, oxygen and sulfur, wherein the latter two aromatic rings maybe substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,C₁-C₃haloalkoxy, halogen, cyano or by nitro; or R₀, together with theadjacent substituents R₁, R₂ and R₃, forms a saturated or unsaturatedC₃-C₆hydrocarbon bridge that may be interrupted by 1 or 2 hetero atomsselected from the group consisting of nitrogen, oxygen and sulfur and/ormay be substituted by C₁-C₄alkyl; R₁, R₂ and R₃ are each independentlyof the others hydrogen, halogen, C₁-C₆alkyl, C₂-C₆-alkenyl,C₂-C₆alkynyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl,C₁-C₆alkoxycarbonyl-C₂-C₆alkenyl, C₁-C₆alkylcarbonyl-C₂-C₆alkenyl,cyano-C₂-C₆alkenyl, nitro-C₂-C₆-alkenyl, C₂-C₆haloalkynyl,C₁-C₆alkoxycarbonyl-C₂-C₆alkynyl, C₁-C₆alkylcarbonyl-C₂-C₆-alkynyl,cyano-C₂-C₆alkynyl, nitro-C₂-C₆alkynyl, C₃-C₆halocycloalkyl,hydroxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆alkylthio-C₁-C₆alkyl,cyano, C₁-C₄alkylcarbonyl, C₁-C₆alkoxycarbonyl, hydroxy, C₁-C₁₀alkoxy,C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C₁-C₆haloalkoxy, C₃-C₆-haloalkenyloxy,C₁-C₆alkoxy-C₁-C₆alkoxy, mercapto, C₁-C₆alkylthio, C₁-C₆haloalkylthio,C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, nitro, amino, C₁-C₆alkylamino,di(C₁-C₆alkyl)amino or phenoxy in which the phenyl ring may besubstituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃-alkoxy,C₁-C₃haloalkoxy, halogen, cyano or by nitro; R₂ also may be phenyl,naphthyl or a 5- or 6-membered aromatic ring that may contain 1 or 2hetero atoms selected from the group consisting of nitrogen, oxygen andsulfur, wherein the phenyl ring, the naphthyl ring system and the 5- or6-membered aromatic ring may be substituted by halogen, C₃-C₈cycloalkyl,hydroxy, mercapto, amino, cyano, nitro or by formyl; and/or the phenylring, the naphthyl ring system and the 5- or 6-membered aromatic ringmay be substituted by C₁-C₆alkyl, C₁-C₆alkoxy, hydroxy-C₁-C₆alkyl,C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆-alkoxy-C₁-C₆alkoxy, C₁-C₆alkylcarbonyl,C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl,mono-C₁-C₆alkylamino, di(C₁-C₆alkyl)amino, C₁-C₆alkylcarbonylamino,C₁-C₆alkylcarbonyl-(C₁-C₆alkyl)amino, C₂-C₆alkenyl, C₃-C₆alkenyloxy,hydroxy-C₃-C₆alkenyl, C₁-C₆alkoxy-C₂-C₆-alkenyl,C₁-C₆alkoxy-C₃-C₆alkenyloxy, C₂-C₆alkenylcarbonyl, C₂-C₆alkenylthio,C₂-C₆alkenylsulfinyl, C₂-C₆alkenylsulfonyl, mono- ordi-(C₂-C₆alkenyl)amino, C₁-C₆alkyl(C₃-C₆alkenyl)-amino,C₂-C₆alkenylcarbonylamino, C₂-C₆alkenylcarbonyl(C₁-C₆alkyl)amino,C₂-C₆alkynyl, C₃-C₆alkynyloxy, hydroxy-C₃-C₆alkynyl,C₁-C₆alkoxy-C₃-C₆alkynyl, C₁-C₆alkoxy-C₄-C₆alkynyloxy,C₂-C₆alkynylcarbonyl, C₂-C₆alkynylthio, C₂-C₆alkynylsulfinyl,C₂-C₆alkynylsulfonyl, mono- or di-(C₃-C₆alkynyl)amino,C₁-C₆alkyl(C₃-C₆alkynyl)amino, C₂-C₆alkynylcarbonylamino or byC₂-C₆alkynylcarbonyl(C₁-C₆alkyl)amino; and/or the phenyl ring, thenaphthyl ring system and the 5- or 6-membered aromatic ring may besubstituted by halo-substituted C₁-C₆alkyl, C₁-C₆alkoxy,hydroxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkoxy,C₁-C₆alkylcarbonyl, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl,C₁-C₆alkylsulfonyl, mono-C₁-C₆alkylamino, di(C₁-C₆alkyl)amino,C₁-C₆alkylcarbonylamino, C₁-C₆alkylcarbonyl(C₁-C₆alkyl)amino,C₂-C₆alkenyl, C₃-C₆alkenyloxy, hydroxy-C₃-C₆alkenyl,C₁-C₆alkoxy-C₂-C₆alkenyl, C₁-C₆alkoxy-C₃-C₆alkenyloxy,C₂-C₆alkenylcarbonyl, C₂-C₆alkenylthio, C₂-C₆alkenylsulfinyl,C₂-C₆alkenylsulfonyl, mono- or di-(C₂-C₆alkenyl)amino,C₁-C₆alkyl-(C₃-C₆alkenyl)amino, C₂-C₆alkenylcarbonylamino,C₂-C₆alkenylcarbonyl(C₁-C₆alkyl)amino, C₂-C₆alkynyl, C₃-C₆alkynyloxy,hydroxy-C₃-C₆alkynyl, C₁-C₆alkoxy-C₃-C₆alkynyl,C₁-C₆alkoxy-C₄-C₆alkynyloxy, C₂-C₆alkynylcarbonyl, C₂-C₆alkynylthio,C₂-C₆alkynylsulfinyl, C₂-C₆alkynylsulfonyl, mono- ordi-(C₃-C₆alkynyl)amino, C₁-C₆alkyl(C₃-C₆alkynyl)amino,C₂-C₆alkynylcarbonylamino or C₂-C₆alkynylcarbonyl(C₁-C₆alkyl)amino;and/or the phenyl ring, the naphthyl ring system and the 5- or6-membered aromatic ring may be substituted by a radical of the formulaCOOR₅₀, CONR₅₁, SO₂NR₅₃R₅₄ or SO₂OR₅₅ wherein R₅₀, R₅₁, R₅₂, R₅₃, R₅₄and R₅₅ are each independently of the others C₁-C₆alkyl, C₂-C₆alkenyl orC₃-C₆alkynyl or halo-, hydroxy-, alkoxy-, mercapto-, amino-, cyano-,nitro-, alkylthio-, alkylsulfinyl- or alkylsulfonyl-substitutedC₁-C₆alkyl, C₂-C₆alkenyl or C₃-C₆alkynyl; n is 0, 1 or 2; R₄ and R₅ areeach independently of the other hydrogen, C₁-C₁₂alkyl, C₁-C₁₋₂haloalkyl,C₂-C₈-alkenyl, C₂-C₈alkynyl, C₁-C₁₀alkoxy-C₁-C₈alkyl,poly-C₁-C₁₀alkoxy-C₁-C₈alkyl, C₁-C₁₀alkylthio-C₁-C₈alkyl,C₃-C₈cycloalkyl, C₃-C₈halocycloalkyl, 4- to 8-membered heterocyclyl,phenyl, α- or β-naphthyl, phenyl-C₁-C₆alkyl, α- orβ-naphthyl-C₁-C₆alkyl, 5- or 6-membered heteroaryl or 5- or 6-memberedheteroaryl-C₁-C₆alkyl, wherein those aromatic and heteroaromatic ringsmay be substituted by halogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy,C₁-C₆haloalkoxy, nitro or by cyano; or R₄ and R₅, together with thenitrogen atoms to which they are bonded, form a saturated or unsaturated5- to 8-membered heterocyclic ring that 1) may be interrupted by oxygen,sulfur or by —NR₁₄— and/or may be substituted by halogen, C₁-C₁₀alkyl,C₁-C₁₀haloalkyl, hydroxy, C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy,C₁-C₆haloalkoxy, mercapto, C₁-C₆alkylthio, C₃-C₇-cycloalkyl, heteroaryl,heteroaryl-C₁-C₆alkyl, phenyl, phenyl-C₁-C₆alkyl or by benzyloxy,wherein the phenyl rings of the last three substituents may in turn besubstituted by halogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy,C₁-C₆haloalkoxy or by nitro, and/or 2) may contain a fused orspiro-bound alkylene or alkenylene chain having from 2 to 6 carbon atomsthat is optionally interrupted by oxygen or by sulfur, or at least onering atom of the saturated or unsaturated heterocyclic ring bridges thatalkylene or alkenylene chain; R₁₄ is hydrogen, C₁-C₄alkyl,C₁-C₆alkylcarbonyl, C₁-C₆alkylsulfonyl, C₃-C₆alkenyl or C₃-C₆alkynyl;and G is hydrogen, a metal ion equivalent or an ammonium, sulfonium orphosphonium cation, which process comprises reacting a compound offormula II

wherein R₀, R₁, R₂, R₃ and n are as defined hereinbefore; R₆ is R₈R₉N—;R₇ is R₁₀R₁₁N— or R₁₂O—; and R₈, R₉, R₁₀, R₁₁ and R₁₂ are eachindependently of the others hydrogen, C₁-C₆-alkyl, C₁-C₆haloalkyl,C₃-C₆alkenyl or benzyl, wherein the phenyl ring of the benzyl group maybe substituted by C₁-C₄alkyl, halogen, C₁-C₄haloalkyl, C₁-C₄alkoxy or bynitro, in an inert organic solvent, optionally in the presence of abase, with a compound of formula IV, IVa or IVb

wherein R₄ and R₅ are as defined hereinbefore and H.Hal is a hydrogenhalide, and optionally converting the resulting compound of formula Iwherein G is a metal ion equivalent or an ammonium cation, by saltconversion into the corresponding salt of formula I wherein G is asulfonium or phosphonium cation, or by treatment with a Brönsted acidinto the corresponding compound of formula I wherein G is hydrogen.
 2. Aprocess for the preparation of a compound of formula I according toclaim 1, wherein R₀ is, each independently of any other, halogen,C₁-C₆alkyl, C₁-C₆haloalkyl, hydroxy, C₁-C₆-alkoxy, nitro, amino,C₁-C₆alkylamino, di(C₁-C₆alkyl)amino, C₁-C₆alkylcarbonylamino,C₁-C₆-alkylsulfonylamino, C₁-C₆alkylaminosulfonyl, C₁-C₄alkylcarbonyl,C₁-C₆alkoxycarbonyl or carboxy; and R₁, R₂ and R₃ are each independentlyof the others hydrogen, halogen, C₁-C₆alkyl, C₂-C₆-alkenyl,C₂-C₆alkynyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl,C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl, C₁-C₆alkoxy-C₁-C₆alkyl,C₁-C₆alkylthio-C₁-C₆alkyl, cyano, C₁-C₄alkylcarbonyl,C₁-C₆alkoxycarbonyl, hydroxy, C₁-C₁₀alkoxy, C₃-C₆alkenyloxy,C₃-C₆alkynyloxy, C₁-C₆haloalkoxy, C₃-C₆haloalkenyloxy,C₁-C₆alkoxy-C₁-C₆alkoxy, mercapto, C₁-C₆alkylthio, C₁-C₆haloalkylthio,C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, nitro, amino, C₁-C₄alkylamino ordi(C₁-C₄alkyl)amino.
 3. A process for the preparation of a compound offormula Ia

wherein R₀, R₁, R₂, R₃, R₄, R₅ and n are as defined in claim 1; G₀ is agroup —C(O)—R₃₀, —C(X₁)—X₂—R₃₁, —C(X₃)—N(R₃₂)—R₃₃, —SO₂—R₃₄ or—P(X₄)(R₃₅)—R₃₆; X₁, X₂, X₃ and X₄ are each independently of the othersoxygen or sulfur; R₃₀ is unsubstituted or halo-substituted C₁-C₂₀alkyl,C₂-C₂₀alkenyl, C₁-C₈alkoxy-C₁-C₈alkyl, C₁-C₈alkylthio-C₁-C₈alkyl,poly-C₁-C₈alkoxy-C₁-C₈alkyl or unsubstituted or halo-, C₁-C₆alkyl- orC₁-C₆alkoxy-substituted C₃-C₈cycloalkyl in which optionally at least onering member has been replaced by oxygen and/or by sulfur,C₃-C₆cycloalkyl-C₁-C₆alkyl, heterocyclyl-C₁-C₆-alkyl,heteroaryl-C₁-C₆alkyl, unsubstituted or halo-, cyano-, nitro-,C₁-C₆alkyl-, C₁-C₆alkoxy-, C₁-C₆haloalkyl-, C₁-C₆haloalkoxy-,C₁-C₆alkylthio- or C₁-C₆alkylsulfonyl-substituted phenyl, unsubstitutedor halo-, nitro-, cyano-, C₁-C₆alkyl-, C₁-C₆alkoxy-, C₁-C₆haloalkyl- orC₁-C₆haloalkoxy-substituted phenyl-C₁-C₆alkyl, unsubstituted or halo- orC₁-C₆alkyl-substituted heteroaryl, unsubstituted or halo- orC₁-C₆alkyl-substituted phenoxy-C₁-C₆alkyl, or unsubstituted or halo-,amino- or C₁-C₆alkyl-substituted heteroaryloxy-C₁-C₆alkyl; R₃₁ isunsubstituted or halo-substituted C₁-C₂₀alkyl, C₂-C₂₀alkenyl,C₁-C₈alkoxy-C₂-C₈alkyl, poly-C₁-C₈alkoxy-C₂-C₈alkyl, unsubstituted orhalo-, C₁-C₆alkyl- or C₁-C₆alkoxy-substituted C₃-C₈cycloalkyl,C₃-C₆cycloalkyl-C₁-C₆alkyl, heterocyclyl-C₁-C₆alkyl,heteroaryl-C₁-C₆alkyl, unsubstituted or halo-, cyano-, nitro-,C₁-C₆alkyl-, C₁-C₆alkoxy-, C₁-C₆haloalkyl- orC₁-C₆-haloalkoxy-substituted phenyl or benzyl; R₃₂ and R₃₃ are eachindependently of the other hydrogen, unsubstituted or halo-substitutedC₁-C₈alkyl, C₃-C₈cycloalkyl, C₁-C₈alkoxy, C₃-C₈alkenyl,C₁-C₈alkoxy-C₁-C₈alkyl, unsubstituted or halo-, C₁-C₈haloalkyl-,C₁-C₈alkyl- or C₁-C₈alkoxy-substituted phenyl or benzyl; or R₃₂ and R₃₃together form a C₃-C₆alkylene chain in which a carbon atom hasoptionally been replaced by oxygen or by sulfur; R₃₄ is unsubstituted orhalo-substituted C₁-C₈alkyl, C₃-C₈alkenyl, C₃-C₈haloalkenyl,C₃-C₈-alkynyl, C₃-C₈haloalkynyl, or unsubstituted or halo-, C₁-C₆alkyl-,C₁-C₆alkoxy-, C₁-C₄haloalkyl-, C₁-C₄haloalkoxy-, cyano- ornitro-substituted phenyl or benzyl; R₃₅ and R₃₆ are each independentlyof the other unsubstituted or halo-substituted C₁-C₈alkyl, C₁-C₈alkoxy,C₁-C₈alkylamino, di(C₁-C₈alkyl)amino, C₁-C₈alkylthio, C₂-C₈alkenylthio,C₃-C₇-cycloalkylthio, or unsubstituted or halo-, nitro-, cyano-,C₁-C₄alkoxy-, C₁-C₄haloalkoxy-, C₁-C₄alkylthio-, C₁-C₄haloalkylthio-,C₁-C₄alkyl- or C₁-C₄haloalkyl-substituted phenyl, phenoxy or phenylthio,which process comprises reacting a compound of formula I prepared inaccordance with claim 1, directly in the reaction solution in a one-potreaction without isolation, optionally in the presence of anacid-binding agent or a catalyst, with an electrophile of formula XII orXIId G_(0-L)  (XII) or R₃₂—N═C═X₃  (XIId), wherein G₀, R₃₂ and X₃ are asdefined hereinbefore except that R₃₂ is not hydrogen, and L is a leavinggroup.
 4. A process according to claim 2, wherein R₁, R₂ and R₃ are eachindependently of the others hydrogen, halogen, C₁-C₄alkyl, C₂-C₄alkenyl,C₂-C₄alkynyl, C₁-C₄haloalkyl, C₃- or C₄-haloalkenyl, C₃-C₆cycloalkyl,C₁-C₄alkylcarbonyl, C₁-C₆alkoxycarbonyl, hydroxy, C₁-C₄alkoxy, C₃- orC₄-alkenyloxy, C₃- or C₄-alkynyloxy, C₁-C₄haloalkoxy, nitro or amino. 5.A process according to claim 1, wherein R₄ and R₅, together with thenitrogen atoms to which they are bonded, form a saturated orunsaturated, 6- or 7-membered heterocyclic ring that 1) may beinterrupted once by oxygen or by sulfur and/or 2) may contain a fused orspiro-bound alkylene chain having from 2 to 5 carbon atoms that isoptionally interrupted once or twice by oxygen or by sulfur, or at leastone ring atom of the saturated or unsaturated heterocyclic ring bridgesthat alkylene chain.
 6. A process according to claim 1, which comprisesusing a compound of formula II wherein R₈, R₉, R₁₀, R₁₁ and R₁₂ arehydrogen, C₁-C₆alkyl or benzyl.
 7. A process according to claim 1,wherein the compound of formula IV, IVa or IVb is used in an equimolaramount or, preferably, in an excess of from 5 to 50 mol %, based on thecompound of formula II.
 8. A process according to claim 1, wherein thereaction is carried out at a reaction temperature of from 0° to 200° C.9. A process according to claim 1, which comprises using as the inertorganic solvent for the reaction an aromatic, aliphatic orcycloaliphatic hydrocarbon, halogenated hydrocarbon, an ether, nitrile,dialkyl sulfoxide, amide or lactam, an alcohol, glycol or polyalcohol, acarboxylic acid, or a mixture of such solvents.
 10. A process accordingto claim 9, which comprises using as the solvent toluene, one of thexylene isomers ortho-, meta- and para-xylene, methylcyclohexane,chlorobenzene or one of the dichlorobenzene isomers 1,2-, 1,3- and1,4-dichlorobenzene.
 11. A process according to claim 1, which comprisescarrying out the condensation reaction in an inert gas atmosphere.
 12. Aprocess according to claim 1, which comprises carrying out the reactionof a compound of formula II with a compound of formula IV with orwithout the addition of a base.
 13. A process according to claim 1,which comprises carrying out the reaction of a compound of formula IIwith a compound of formula IVa or IVb in the presence of a base.
 14. Aprocess according to claim 13, which comprises using as base a tertiaryamine, pyridine, alkali metal alcoholate, or alkali metal or alkalineearth metal hydride, hydroxide, carbonate or hydrogen carbonate.
 15. Aprocess according to claim 14, which comprises using the base incatalytic amounts or in a molar excess of up to 5, based on the compoundof formula II.
 16. The use of a compound of formula I according to claim1 prepared in accordance with the invention, wherein G is hydrogen, ametal ion equivalent or an ammonium, sulfonium or phosphonium cation,for the ‘in situ’ preparation of a compound of formula Ia wherein G₀ isa group —C(O)—R₃₀, —C(X₁)—X₂—R₃₁, —C(X₃)—N(R₃₂)—R₃₃, —SO₂—R₃₄ or—P(X₄)(R₃₅)—R₃₆; and R₃₀, R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆, X₁, X₂, X₃ andX₄ are as defined hereinbefore.
 17. A compound of formula I

wherein R₀ is, each independently of any other, halogen, C₁-C₆alkyl,C₂-C₆alkenyl, C₂-C₆-alkynyl, C₁-C₆haloalkyl, cyano-C₁-C₆alkyl,C₂-C₆haloalkenyl, cyano-C₂-C₆alkenyl, C₂-C₆haloalkynyl,cyano-C₂-C₆alkynyl, hydroxy, hydroxy-C₁-C₆alkyl, C₁-C₆alkoxy, nitro,amino, C₁-C₆-alkylamino, di(C₁-C₆alkyl)amino, C₁-C₆alkylcarbonylamino,C₁-C₆alkylsulfonylamino, C₁-C₆-alkylaminosulfonyl, C₁-C₆alkylcarbonyl,C₁-C₆alkylcarbonyl-C₁-C₆alkyl, C₁-C₆alkoxycarbonyl-C₁-C₆alkyl,C₁-C₆alkylcarbonyl-C₂-C₆alkenyl, C₁-C₆alkoxycarbonyl-C₂-C₆alkenyl,C₁-C₆-alkylcarbonyl-C₂-C₆alkynyl, C₁-C₆alkoxycarbonyl-C₂-C₆alkynyl,C₁-C₆alkoxycarbonyl, cyano, carboxyl, phenyl or an aromatic ring thatcontains 1 or 2 hetero atoms selected from the group consisting ofnitrogen, oxygen and sulfur, wherein the latter two aromatic rings maybe substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,C₁-C₃haloalkoxy, halogen, cyano or by nitro; or R₀, together with theadjacent substituents R₁, R₂ and R₃, forms a saturated or unsaturatedC₃-C₆hydrocarbon bridge that may be interrupted by 1 or 2 hetero atomsselected from the group consisting of nitrogen, oxygen and sulfur and/ormay be substituted by C₁-C₄alkyl; R₁, R₂ and R₃ are each independentlyof the others hydrogen, halogen, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl,C₃-C₆cycloalkyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl,C₁-C₆alkoxycarbonyl-C₂-C₆alkenyl, C₁-C₆alkylcarbonyl-C₂-C₆alkenyl,cyano-C₂-C₆alkenyl, nitro-C₂-C₆alkenyl, C₂-C₆haloalkynyl,C₁-C₆alkoxycarbonyl-C₂-C₆alkynyl, C₁-C₆alkylcarbonyl-C₂-C₆alkynyl,cyano-C₂-C₆alkynyl, nitro-C₂-C₆alkynyl, C₃-C₆-halocycloalkyl,hydroxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆alkylthio-C₁-C₆alkyl,cyano, C₁-C₄alkylcarbonyl, C₁-C₆alkoxycarbonyl, hydroxy, C₁-C₁₀alkoxy,C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C₁-C₆haloalkoxy, C₃-C₆haloalkenyloxy,C₁-C₆alkoxy-C₁-C₆alkoxy, mercapto, C₁-C₆alkylthio, C₁-C₆haloalkylthio,C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, nitro, amino, C₁-C₆alkylamino,di(C₁-C₆alkyl)-amino or phenoxy in which the phenyl ring may besubstituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy,halogen, cyano or by nitro; R₂ also may be phenyl, naphthyl or a 5- or6-membered aromatic ring that may contain 1 or 2 hetero atoms selectedfrom the group consisting of nitrogen, oxygen and sulfur, wherein thephenyl ring, the naphthyl ring system and the 5- or 6-membered aromaticring may be substituted by halogen, C₃-C₈cycloalkyl, hydroxy, mercapto,amino, cyano, nitro or by formyl; and/or the phenyl ring, the naphthylring system and the 5- or 6-membered aromatic ring may be substituted byC₁-C₆alkyl, C₁-C₆alkoxy, hydroxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl,C₁-C₆-alkoxy-C₁-C₆alkoxy, C₁-C₆alkylcarbonyl, C₁-C₆alkylthio,C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, mono-C₁-C₆alkylamino,di(C₁-C₆alkyl)amino, C₁-C₆alkylcarbonylamino,C₁-C₆alkylcarbonyl-(C₁-C₆alkyl)amino, C₂-C₆alkenyl, C₃-C₆alkenyloxy,hydroxy-C₃-C₆alkenyl, C₁-C₆alkoxy-C₂-C₆-alkenyl,C₁-C₆alkoxy-C₃-C₆alkenyloxy, C₂-C₆alkenylcarbonyl, C₂-C₆alkenylthio,C₂-C₆-alkenylsulfinyl, C₂-C₆alkenylsulfonyl, mono- ordi-(C₂-C₆alkenyl)amino, C₁-C₆alkyl(C₃-C₆-alkenyl)amino,C₂-C₆alkenylcarbonylamino, C₂-C₆alkenylcarbonyl(C₁-C₆alkyl)amino,C₂-C₆-alkynyl, C₃-C₆alkynyloxy, hydroxy-C₃-C₆alkynyl,C₁-C₆alkoxy-C₃-C₆alkynyl, C₁-C₆alkoxy-C₄-C₆alkynyloxy,C₂-C₆alkynylcarbonyl, C₂-C₆alkynylthio, C₂-C₆alkynylsulfinyl,C₂-C₆alkynylsulfonyl, mono- or di-(C₃-C₆alkynyl)amino,C₁-C₆alkyl(C₃-C₆alkynyl)amino, C₂-C₆alkynylcarbonylamino or byC₂-C₆alkynylcarbonyl(C₁-C₆alkyl)amino; and/or the phenyl ring, thenaphthyl ring system and the 5- or 6-membered aromatic ring may besubstituted by halo-substituted C₁-C₆alkyl, C₁-C₆alkoxy,hydroxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkoxy,C₁-C₆alkylcarbonyl, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl,C₁-C₆alkylsulfonyl, mono-C₁-C₆alkylamino, di(C₁-C₆alkyl)amino,C₁-C₆alkylcarbonylamino, C₁-C₆alkylcarbonyl(C₁-C₆alkyl)amino,C₂-C₆alkenyl, C₃-C₆alkenyloxy, hydroxy-C₃-C₆alkenyl,C₁-C₆alkoxy-C₂-C₆alkenyl, C₁-C₆alkoxy-C₃-C₆alkenyloxy,C₂-C₆alkenylcarbonyl, C₂-C₆alkenylthio, C₂-C₆alkenylsulfinyl,C₂-C₆alkenylsulfonyl, mono- or di-(C₂-C₆alkenyl)amino,C₁-C₆alkyl-(C₃-C₆alkenyl)amino, C₂-C₆alkenylcarbonylamino,C₂-C₆alkenylcarbonyl(C₁-C₆alkyl)amino, C₂-C₆alkynyl, C₃-C₆alkynyloxy,hydroxy-C₃-C₆alkynyl, C₁-C₆alkoxy-C₃-C₆alkynyl,C₁-C₆alkoxy-C₄-C₆alkynyloxy, C₂-C₆alkynylcarbonyl, C₂-C₆alkynylthio,C₂-C₆alkynylsulfinyl, C₂-C₆alkynylsulfonyl, mono- ordi-(C₃-C₆alkynyl)amino, C₁-C₆alkyl(C₃-C₆alkynyl)amino,C₂-C₆alkynylcarbonylamino or C₂-C₆alkynylcarbonyl(C₁-C₆alkyl)amino;and/or the phenyl ring, the naphthyl ring system and the 5- or6-membered aromatic ring may be substituted by a radical of the formulaCOOR₅₀, CONR₅₁, SO₂NR₅₃R₅₄ or SO₂OR₅₅ wherein R₅₀, R₅₁, R₅₂, R₅₃, R₅₄and R₅₅ are each independently of the others C₁-C₆alkyl, C₂-C₆alkenyl orC₃-C₆alkynyl or halo-, hydroxy-, alkoxy-, mercapto-, amino-, cyano-,nitro-, alkylthio-, alkylsulfinyl- or alkylsulfonyl-substitutedC₁-C₆alkyl, C₂-C₆alkenyl or C₃-C₆alkynyl; n is 1 or 2; R₄ and R₅,together with the nitrogen atoms to which they are bonded, form asaturated or unsaturated 5- to 8-membered heterocyclic ring that 1) isinterrupted by oxygen, sulfur or by —NR₁₄— and may be substituted byhalogen, C₁-C₁₀alkyl, C₁-C₁₀haloalkyl, hydroxy, C₁-C₆alkoxy,C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆haloalkoxy, mercapto, C₁-C₆alkylthio,C₃-C₇-cycloalkyl, heteroaryl, heteroaryl-C₁-C₆alkyl, phenyl,phenyl-C₁-C₆alkyl or by benzyloxy, wherein the phenyl rings of the lastthree substituents may in turn be substituted by halogen, C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy or by nitro, and 2) maycontain a fused or spiro-bound alkylene or alkenylene chain having from2 to 6 carbon atoms that is optionally interrupted by oxygen or bysulfur, or at least one ring atom of the saturated or unsaturatedheterocyclic ring bridges that alkylene or alkenylene chain; R₁₄ ishydrogen, C₁-C₄alkyl, C₁-C₆alkylcarbonyl, C₁-C₆alkylsulfonyl,C₃-C₆alkenyl or C₃-C₆alkynyl; and G is hydrogen or a metal ionequivalent or an ammonium, sulfonium or phosphonium cation.
 18. Acompound of formula Ia

wherein R₀ is, each independently of the any other, halogen, C₁-C₆alkyl,C₂-C₆alkenyl, C₂-C₆-alkynyl, C₁-C₆haloalkyl, cyano-C₁-C₆alkyl,C₂-C₆haloalkenyl, cyano-C₂-C₆alkenyl, C₂-C₆haloalkynyl,cyano-C₂-C₆alkynyl, hydroxy, hydroxy-C₁-C₆alkyl, C₁-C₆alkoxy, nitro,amino, C₁-C₆alkylamino, di(C₁-C₆alkyl)amino, C₁-C₆alkylcarbonylamino,C₁-C₆alkylsulfonylamino, C₁-C₆alkylaminosulfonyl, C₁-C₆alkylcarbonyl,C₁-C₆alkylcarbonyl-C₁-C₆alkyl, C₁-C₆alkoxycarbonyl-C₁-C₆alkyl,C₁-C₆alkylcarbonyl-C₂-C₆alkenyl, C₁-C₆alkoxycarbonyl-C₂-C₆-alkenyl,C₁-C₆alkylcarbonyl-C₂-C₆alkynyl, C₁-C₆alkoxycarbonyl-C₂-C₆alkynyl,C₁-C₆alkoxycarbonyl, cyano, carboxyl, phenyl or an aromatic ring thatcontains 1 or 2 hetero atoms selected from the group consisting ofnitrogen, oxygen and sulfur, wherein the latter two aromatic rings maybe substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,C₁-C₃haloalkoxy, halogen, cyano or by nitro; or R₀, together with theadjacent substituents R₁, R₂ and R₃, forms a saturated or unsaturatedC₃-C₆hydrocarbon bridge that may be interrupted by 1 or 2 hetero atomsselected from the group consisting of nitrogen, oxygen and sulfur and/ormay be substituted by C₁-C₄alkyl; R₁, R₂ and R₃ are each independentlyof the others hydrogen, halogen, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl,C₃-C₆cycloalkyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl,C₁-C₆alkoxycarbonyl-C₂-C₆alkenyl, C₁-C₆alkylcarbonyl-C₂-C₆alkenyl,cyano-C₂-C₆alkenyl, nitro-C₂-C₆alkenyl, C₂-C₆haloalkynyl,C₁-C₆alkoxycarbonyl-C₂-C₆alkynyl, C₁-C₆alkylcarbonyl-C₂-C₆alkynyl,cyano-C₂-C₆alkynyl, nitro-C₂-C₆alkynyl, C₃-C₆halocycloalkyl,hydroxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆alkylthio-C₁-C₆alkyl,cyano, C₁-C₄alkylcarbonyl, C₁-C₆alkoxycarbonyl, hydroxy, C₁-C₁₀alkoxy,C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C₁-C₆haloalkoxy, C₃-C₆haloalkenyloxy,C₁-C₆alkoxy-C₁-C₆alkoxy, mercapto, C₁-C₆alkylthio, C₁-C₆haloalkylthio,C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, nitro, amino, C₁-C₆alkylamino,di(C₁-C₆alkyl)amino or phenoxy in which the phenyl ring may besubstituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy,halogen, cyano or by nitro; R₂ also may be phenyl, naphthyl or a 5- or6-membered aromatic ring that may contain 1 or 2 hetero atoms selectedfrom the group consisting of nitrogen, oxygen and sulfur, wherein thephenyl ring, the naphthyl ring system and the 5- or 6-membered aromaticring may be substituted by halogen, C₃-C₈cycloalkyl, hydroxy, mercapto,amino, cyano, nitro or by formyl; and/or the phenyl ring, the naphthylring system and the 5- or 6-membered aromatic ring may be substituted byC₁-C₆alkyl, C₁-C₆alkoxy, hydroxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl,C₁-C₆-alkoxy-C₁-C₆alkoxy, C₁-C₆alkylcarbonyl, C₁-C₆alkylthio,C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, mono-C₁-C₆alkylamino,di(C₁-C₆alkyl)amino, C₁-C₆alkylcarbonylamino,C₁-C₆alkylcarbonyl-(C₁-C₆alkyl)amino, C₂-C₆alkenyl, C₃-C₆alkenyloxy,hydroxy-C₃-C₆alkenyl, C₁-C₆alkoxy-C₂-C₆-alkenyl,C₁-C₆alkoxy-C₃-C₆alkenyloxy, C₂-C₆alkenylcarbonyl, C₂-C₆alkenylthio,C₂-C₆alkenylsulfinyl, C₂-C₆alkenyisulfonyl, mono- ordi-(C₂-C₆alkenyl)amino, C₁-C₆alkyl(C₃-C₆alkenyl)-amino,C₂-C₆alkenylcarbonylamino, C₂-C₆alkenylcarbonyl(C₁-C₆alkyl)amino,C₂-C₆alkynyl, C₃-C₆alkynyloxy, hydroxy-C₃-C₆alkynyl,C₁-C₆alkoxy-C₃-C₆alkynyl, C₁-C₆alkoxy-C₄-C₆alkynyloxy,C₂-C₆alkynylcarbonyl, C₂-C₆alkynylthio, C₂-C₆alkynylsulfinyl,C₂-C₆alkynylsulfonyl, mono- or di-(C₃-C₆alkynyl)amino,C₁-C₆alkyl(C₃-C₆alkynyl)amino, C₂-C₆alkynylcarbonylamino or byC₂-C₆alkynylcarbonyl(C₁-C₆alkyl)amino; and/or the phenyl ring, thenaphthyl ring system and the 5- or 6-membered aromatic ring may besubstituted by halo-substituted C₁-C₆alkyl, C₁-C₆alkoxy,hydroxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkoxy,C₁-C₆alkylcarbonyl, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl,C₁-C₆alkylsulfonyl, mono-C₁-C₆alkylamino, di(C₁-C₆alkyl)amino,C₁-C₆alkylcarbonylamino, C₁-C₆alkylcarbonyl(C₁-C₆alkyl)amino,C₂-C₆alkenyl, C₃-C₆alkenyloxy, hydroxy-C₃-C₆alkenyl,C₁-C₆alkoxy-C₂-C₆alkenyl, C₁-C₆alkoxy-C₃-C₆alkenyloxy,C₂-C₆alkenylcarbonyl, C₂-C₆alkenylthio, C₂-C₆alkenylsulfinyl,C₂-C₆alkenylsulfonyl, mono- or di-(C₂-C₆alkenyl)amino,C₁-C₆alkyl-(C₃-C₆alkenyl)amino, C₂-C₆alkenylcarbonylamino,C₂-C₆alkenylcarbonyl(C₁-C₆alkyl)amino, C₂-C₆alkynyl, C₃-C₆alkynyloxy,hydroxy-C₃-C₆alkynyl, C₁-C₆alkoxy-C₃-C₆alkynyl,C₁-C₆alkoxy-C₄-C₆alkynyloxy, C₂-C₆alkynylcarbonyl, C₂-C₆alkynylthio,C₂-C₆alkynylsulfinyl, C₂-C₆alkynylsulfonyl, mono- ordi-(C₃-C₆alkynyl)amino, C₁-C₆alkyl(C₃-C₆alkynyl)amino,C₂-C₆alkynylcarbonylamino or C₂-C₆alkynylcarbonyl(C₁-C₆alkyl)amino;and/or the phenyl ring, the naphthyl ring system and the 5- or6-membered aromatic ring may be substituted by a radical of the formulaCOOR₅₀, CONR₅₁, SO₂NR₅R₅₄ or SO₂₀R₅ wherein R₅₀, R₅₁, R₅₂, R₅₃, R₅₄ andR₅₅ are each independently of the others C₁-C₆alkyl, C₂-C₆alkenyl orC₃-C₆alkynyl or halo-, hydroxy-, alkoxy-, mercapto-, amino-, cyano-,nitro-, alkylthio-, alkylsulfinyl- or alkylsulfonyl-substitutedC₁-C₆alkyl, C₂-C₆alkenyl or C₃-C₆alkynyl; n is 1 or 2; R₄ and R₅,together with the nitrogen atoms to which they are bonded, form asaturated or unsaturated 5- to 8-membered heterocyclic ring that 1) isinterrupted by oxygen, sulfur or by —NR₁₄— and may be substituted byhalogen, C₁-C₁₀alkyl, C₁-C₁₀haloalkyl, hydroxy, C₁-C₆alkoxy,C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆haloalkoxy, mercapto, C₁-C₆alkylthio,C₃-C₇-cycloalkyl, heteroaryl, heteroaryl-C₁-C₆alkyl, phenyl,phenyl-C₁-C₆alkyl or by benzyloxy, wherein the phenyl rings of the lastthree substituents may in turn by substituted by halogen, C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy or by nitro, and 2) maycontain a fused or spiro-bound alkylene or alkenylene chain having from2 to 6 carbon atoms that is optionally interrupted by oxygen or bysulfur, or at least one ring atom of the saturated or unsaturatedheterocyclic ring bridges that alkylene or alkenylene chain; R₁₄ ishydrogen, C₁-C₄alkyl, C₁-C₆alkylcarbonyl, C₁-C₆alkylsulfonyl,C₃-C₆alkenyl or C₃-C₆alkynyl; and G₀ is a group —C(O)—R₃₀, —C(X₁)—X₂—R₃₁or —SO₂—R₃₄; X₁, X₂, X₃ and X₄ are each independently of the othersoxygen or sulfur; R₃₀ is unsubstituted or halo-substituted C₁-C₂₀alkyl,C₂-C₂₀alkenyl, C₁-C₈alkoxy-C₁-C₈alkyl, C₁-C₈alkylthio-C₁-C₈alkyl,poly-C₁-C₈alkoxy-C₁-C₈alkyl or unsubstituted or halo-substitutedC₃-C₈cycloalkyl, C₃-C₆cycloalkyl-C₁-C₆alkyl, heterocyclyl-C₁-C₆alkyl,heteroaryl-C₁-C₆alkyl, unsubstituted or halo-, cyano-, nitro-,C₁-C₆alkyl-, C₁-C₆alkoxy-, C₁-C₆haloalkyl-, C₁-C₆haloalkoxy-,C₁-C₆alkylthio- or C₁-C₆alkylsulfonyl-substituted phenyl, unsubstitutedor halo-, nitro-, cyano-, C₁-C₆alkyl-, C₁-C₆alkoxy-, C₁-C₆haloalkyl- orC₁-C₆haloalkoxy-substituted phenyl-C₁-C₆alkyl, unsubstituted or halo- orC₁-C₆alkyl-substituted heteroaryl, unsubstituted or halo- orC₁-C₆alkyl-substituted phenoxy-C₁-C₆alkyl, or unsubstituted or halo-,amino- or C₁-C₆alkyl-substituted heteroaryloxy-C₁-C₆alkyl; R₃₁ isunsubstituted or halo-substituted C₁-C₂₀alkyl, C₂-C₂₀alkenyl,C₁-C₈alkoxy-C₂-C₈alkyl, poly-C₁-C₈alkoxy-C₂-C₈alkyl, unsubstituted orhalo- or C₁-C₆alkoxy-substituted C₃-C₈cycloalkyl,C₃-C₆cycloalkyl-C₁-C₆alkyl, heterocyclyl-C₁-C₆alkyl,heteroaryl-C₁-C₆alkyl, unsubstituted or halo-, cyano-, nitro-,C₁-C₆-alkyl-, C₁-C₆alkoxy-, C₁-C₆haloalkyl- orC₁-C₆haloalkoxy-substituted phenyl or benzyl; R₃₄ is unsubstituted orhalo-substituted C₁-C₈alkyl, or unsubstituted or halo-, C₁-C₆alkyl-,C₁-C₆-alkoxy-, C₁-C₄haloalkyl-, C₁-C₄haloalkoxy-, cyano- ornitro-substituted phenyl.
 19. A compound of formula II

wherein R₀, R₁, R₂, R₃, R₆, R₇ and n are as defined in claim
 1. 20. Acompound of formula II according to claim 19, wherein R₁, R₂ and R₃ areeach independently of the others hydrogen, halogen, C₁-C₄alkyl,C₁-C₄haloalkyl, C₂-C₄alkenyl, C₂-C₄haloalkenyl, C₂-C₄alkynyl,C₃-C₆cycloalkyl, C₁-C₄alkylcarbonyl, C₁-C₆alkoxycarbonyl, hydroxy,C₁-C₄alkoxy, C₃— or C₄-alkenyloxy, C₃— or C₄-alkynyloxy,C₁-C₄haloalkoxy, nitro or amino.
 21. A compound of formula II accordingto claim 19, wherein R₁ is C₂-C₆alkyl.
 22. A compound of formula IIaccording to claim 19, wherein n is
 0. 23. A compound of formula IIaccording to claim 22, wherein R₁ is C₂-C₄alkyl, C₁-C₄alkoxy,C₂-C₄alkynyl or C₃-C₆cycloalkyl and R₃ is C₁-C₄alkyl, C₁-C₄alkoxy,C₂-C₄alkynyl or C₃-C₆-cycloalkyl sind.
 24. A compound of formula IIaccording to claim 19, wherein R₁ is C₂-C₆alkynyl.
 25. A compound offormula II according to claim 19, wherein R₁ and R₃ are eachindependently of the other C₂-C₆alkyl, C₂-C₆alkynyl, C₁-C₁₀alkoxy orC₃-C₆cycloalkyl.
 26. A compound of formula II according to claim 25,wherein R₁ is C₂-C₆alkyl and R₃ is C₂-C₆alkyl, C₂-C₆alkynyl orC₁-C₁₀alkoxy.
 27. A compound of formula II according to claim 19,wherein R₆ is R₈R₉N— and R₇ is R₁₀R₁₁N—; and R₈, R₉, R₁₀ and R₁₁ are asdefined hereinbefore.